Modified block copolymer composition

ABSTRACT

A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, abrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.

This application is a divisional of copending application Ser. No.432,923, filed on Sept. 30, 1982.

FIELD OF THE INVENTION

The present invention relates to a modified block copolymer compositioncomprising a thermoplastic polymer and a modified block copolymer.

More particularly, the present invention relates to a resinous modifiedblock copolymer composition excellent in impact resistance, adhesion,paint adhesion, weatherability, resistance to heat aging, transparencyand gloss and also to a rubbery or leather-like modified block copolymercomposition excellent in heat resistance, abrasion resistance,compression set resistance, adhesion, transparency, oil resistance,weatherability and resistance to heat aging. Each of the abovementionedcompositions comprises a thermoplastic polymer and a modified blockcopolymer comprising a base block copolymer of a monovinyl substitutedaromatic hydrocarbon polymer block and an olefin compound polymer blockhaving an ethylenic unsaturation degree not exceeding 20%, the baseblock copolymer having a molecular unit containing a carboxylic acidgroup and/or a group derived therefrom grafted thereonto.

DESCRIPTION OF THE PRIOR ART

Recently, thermoplastic resins such as polyamides, thermoplasticpolyesters, thermoplastic polyurethanes, polyoxymethylene resins,polycarbonate resins, polysulfone resins, nitrile resins, polyphenyleneether resins and polyarylene sulfide resins have been widely used formechanical parts and electrical parts for which excellent mechanicalcharacteristics, high heat resistance and good durability are required.Weight reduction of the body of an automobile has been promoted todecrease fuel expenses as one of the energy-saving measures, andthermoplastic resins have attracted attention as light-weight materialsfor automobile parts which have excellent mechanical characteristics anddurability.

However, these thermoplastic resins have some defects and fail tosufficiently satisfy requirements demanded in their application fields.

For example, polyoxymethylene resins and nitrile resins are advantageousin that they have very high tensile strength, flexural strength andflexural modulus, they can provide very tough molded articles and theyare excellent in solvent resistance, but these resins are inferior inpaint adhesion and they cannot advantageously be used as automotiveexterior and interior trims or as exterior decorative materials ofhousehold electrical appliances. Polycarbonate resins have a very highmechanical strength and their impact strength is very high, but theseresins are defective in that the paint adhesion is relatively poor.Furthermore, polyamides, thermoplastic polyesters, polysulfone resins,polyphenylene ether resins and polyarylene sulfide resins have a goodheat resistance and a high mechanical strength, but they are defectivein that the impact resistance is poor.

Block copolymers comprising a monovinyl substituted aromatic hydrocarbonand a conjugated diene compound, especially styrene-butadiene blockcopolymers, are polymeric materials which have recently attractedattentions.

Characteristic properties of these block copolymers differ according tothe content of the monovinyl substituted aromatic hydrocarbon. Morespecifically, a block copolymer having a relatively low content of themonovinyl substituted aromatic hydrocarbon, even though it isunvulcanized, has a good elasticity at room temperature and showsrubbery characteristics. On the other hand, a block copolymer having arelatively high content of the monovinyl substituted aromatichydrocarbon is excellent in transparency and impact resistance and showsresinous characteristics. Moreover, a block copolymer comprising amonovinyl substituted aromatic hydrocarbon and a conjugated dienecompound shows at high temperatures flow characteristics similar tothose of a thermoplastic resin, and this block copolymer is advantageousin that the block copolymer can easily be molded by an ordinary extruderor injection molding machine. However, the above-mentioned blockcopolymers are fatally defective in that the weatherability andresistance to thermal deterioration are poor, and therefore, they havebeen used only in the fields where such properties are not required.Furthermore, shoes prepared from these block copolymers are inferior toclogs prepared from a vinyl chloride polymer or the like in abrasionresistance and resistance to compression set. Accordingly, improvementsof characteristics for overcoming these disadvantages have been desired.

In order to improve the weatherability and resistance to heat aging ofthe above-mentioned block copolymers, hydrogenating the conjugated dienecompound polymer block in the block copolymers have been proposed inCanadian Pat. No. 815,575 and U.S. Pat. No. 3,431,323.

Although the weatherability or resistance to heat aging is improved tosome extent according to this method, the hydrogenated block copolymeris defective in that the adhesion to other materials such as otherplastics, metals, glass and woven fabrics is drastically degraded. Asmeans for eliminating this defect, U.S. Pat. No. 3,792,124, discloses amethod in which an ionically crosslinked product comprising ethylene andan α,β-ethylenically unsaturated carboxylic acid is incorporated intothe hydrogenated block copolymer. However the composition prepared bythe method desclosed in U.S. Pat. No. 3,792,124 does not have asatisfactorily improved adhesion to other materials, and the compositionis defective in that peeling is readily caused in the bonded surfaceunder high humidity conditions or when immersed in water.

As a means for overcoming these defects of thermoplastic resins or blockcopolymers, there has been proposed a method in which a thermoplasticresin is mixed with a block copolymer to form a mixed polymercomposition. For example, there can be mentioned mixed polymercompositions comprising a styrene-butadiene block copolymer, astyrene-isoprene block copolymer or a block copolymer obtained bypartially hydrogenating the above-mentioned copolymer as one componentof different polymers for providing a composition having excellentproperties and a polar polymer such as a polyamide, polyester orpolyurethane as the other component (see U.S. Pat. No. 4,017,558, U.S.Pat. No. 3,975,459, Japanese Patent Application LaidOpen SpecificationNo. 75651/1975, U.S. Pat. No. 4,218,545 and U.S. Pat. No. 4,041,103).However, in these compositions, the block copolymer or hydrogenatedblock copolymer component is poor in compatibility with the polarpolymer and the obtained mixed polymer composition is heterogeneous, andthe properties cannot be satisfactorily improved. Moreover, when themixed polymer composition is laminated with other material such as ametal, the adhesion between the mixed polymer composition and the metalis insufficient and peeling is readily caused.

As is apparent from the foregoing description, although thermoplasticresins and block copolymers comprising a monovinyl substituted aromatichydrocarbon and a conjugated diene compound have various excellentproperties, they cannot be materials sufficiently satisfyingrequirements demanded in the fields where they are actually used.Moreover, the mixtures of different polymers proposed for overcoming thedefects of the thermoplastic resins or block copolymers do not have asatisfactorily improved characteristics. Accordingly, development of apolymer composition having properties required in various fields, forexample, in the fields of mechanical parts, electrical parts, automobileparts, construction materials, sheets and films has been stronglydesired in the art.

It is therefore a primary object of the present invention to provide aresinous modified block copolymer composition which is excellent inimpact resistance, paint adhesion, weatherability, resistance to heataging, transparency, gloss and adhesion. Another object of the presentinvention is to provide a rubbery or leather-like modified blockcopolymer composition which is excellent in heat resistance, abrasionresistance, resistance to compression set, adhesion, weatherability,resistance to heat aging, transparency and oil resistance.

SUMMARY OF THE PRESENT INVENTION

The present inventors have extensively and intensively researchedpolymer compositions comprising different polymers with a view toimproving the compatibility between the different polymers anddeveloping excellent polymer compositions retaining characteristics ofthe respective polymers. As a result, it has been determined that amodified block copolymer comprising a base block copolymer having amonovinyl substituted aromatic hydrocarbon polymer block and an olefincompound polymer block having an ethylenic unsaturation degree notexceeding 20% and a molecular unit containing a carboxylic acid groupand/or a group derived therefrom, which is grafted to the base blockcopolymer, has a good compatibility with thermoplastic polymers such aspolar group-containing polar thermoplastic polymers, polyoxymethylenes,or polycarbonates and that a modified block copolymer compositioncomprising this modified block copolymer and a thermoplastic polymer isexcellent over conventional compositions in mechanical characteristicsand has very excellent weatherability and resistance to heat aging. Thepresent invention has been made based on such novel findings.

More specifically, in accordance with the present invention, there isprovided a modified block copolymer composition comprising:

(a) at least one thermoplastic polymer selected from the groupconsisting of polar thermoplastic polymers each containing at least onepolar functional group, polyoxymethylenes, polycarbonates, modifiedpolycarbonates, polysulfones, modified polysulfones, nitrile polymers,polyphenylene ethers, modified polyphenylene ethers, polyarylenesulfides and modified polyarylene sulfies; and

(b) at least one modified block copolymer comprising a base blockcopolymer of at least one monovinyl substituted aromatic hydrocarbonpolymer block A and at least one olefin compound polymer block B havingan ethylenic unsaturation degree not exceeding 20%, the base blockcopolymer having at least one molecular unit grafted thereonto, with theat least one molecular unit containing at least one member selected froma carboxylic acid group and groups derived therefrom, the polarthermoplastic polymer excluding the modified block copolymer (b).

The modified block copolymer composition of the present invention ischaracterized in that a composition having characteristics of a resin(hereinafter often referred to as "resinous composition"), a compositionhaving characteristics of a rubber (hereinafter often referred to as"rubbery composition") and a composition having characteirsticsintermediate between characteristics of a resin and characteristics of arubber (hereinafter often referred to as "leather-like composition") canbe optionally selected according to an intended use by appropriatelyadjusting the ratio between the components (a) and (b) and the contentof the monovinyl substituted hydrocarbon in the base block copolymer ofthe modified block copolymer. When the composition of the presentinvention is a resinous composition, it is especially excellent inimpact resistance, adhesion, paint adhesion, weatherability, resistanceto heat aging, transparency and gloss, and when the composition of thepresent invention is a rubbery or leather-like compositon, it isespecially excellent in heat resistance, abrasion resistance, resistanceto compression set, adhesion, transparency, oil resistance,weatherability and resistance to heat aging.

In the modified block copolymer composition of the present invention,since the modified block copolymer component (b) contains a reactivecarboxylic acid group or a group derived therefrom in the molecule, whenthe component (a) is a polar thermoplastic polymer containing a polargroup reactive with a carboxylic acid group or a group derivedtherefrom, chemical bonding is caused by mutual reaction of both thecomponents or ionic crosslinkage is formed by both the componentsthrough a metal ion or the like, whereby the component (a) is stronglybonded to the component (b). When the component (a) is a polargroup-free thermoplastic polymer, both the components show an excellentcompatibility with each other because of physical mutual actions.Accordingly, the modified block copolymer composition of the presentinvention is excellent over conventional mixed different polymercompositons having an insufficient impact resistance due to a poormutual compatibility in that the modified block copolymer composition ofthe present invention has excellent mechanical characteristics, andfurthermore, the modified block copolymer composition of the presentinvention has both the characteristics of the component (a) and thecharacteristics of the component (b) the is practically very valuable.Moreover, since the olefin compound polymer block of the modified blockcopolymer has an ethylenic unsaturation degree not exceeding 20%, themodified block copolymer composition of the present invention isexcellent in weatherability and resistance to heat aging overconventional block copolymers having a high ethylenic unsaturationdegree, for example, styrene-butadiene block copolymers.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described in detail.

The component (a) of the modified block copolymer composition of thepresent invention is at least one thermoplastic polymer selected fromthe group consisting of polar thermoplastic polymers each containing atleast one polar functional group, polyoxymethylenes, polycarbonates,modified polycarbonates, polysulfones, modified polysulfones, nitrilepolymers, polyphenylene ethers, modified polyphenylene ethers,polyarylene sulfides and modified polyarylene sulfides, and thecomponent (a) excludes the component (b). As the polar thermoplasticpolymer containing at least one polar functional group, any polymerhaving a functional group capable of chemically linking to or capable ofexhibiting a strong physical mutual action with a carboxylic acid groupand/or a group derived therefrom present in the modified block copolymer(b) can be used. As preferred examples of the functional group, therecan be mentioned an amino group, a hydroxyl group, a thiol group, acarboxyl group, an isocyanate group, an epoxy group and groups derivedtherefrom, such as a urethane group, an ester group, an amide group, anammonium salt group and a metal carboxylate group. Thermoplasticpolymers conatining at least one functional group selected from theforegoing groups are preferably used as the component (a). Thesefunctional groups may be bonded to either the terminals or the sidechains of the polymers. As preferred examples of the polar thermoplasticpolymer containing such polar functional group, there can be mentionedpolyamides, thermoplastic polyesters, thermoplastic polyurethanes, vinylalcohol polymers, vinyl ester polymers and ionomers. These polarthermoplastic polymers will now be described in detail.

As the polyamide, there can be mentioned a polycondensate of adicarboxylic acid and a diamine, a polycondensate of anα-aminocarboxylic acid and a polymer produced by ring-openingpolymerization of a cyclic lactam. More specifically, nylon-6, nylon-66,nylon-610, nylon-11, nylon-12, and copolymers thereof, such asnylon-6/nylon-66 and nylon-6/nylon-12 copolymers, are preferred. Fromthe viewpoint of the processability of the composition, it is preferredthat the number average molecular weight of the polyamide be 200 to30,000, especially 200 to 20,000 and that the melting point of thepolyamide be 150° to 270° C., especially 150° to 220° C. In the presentinvention, not only one polyamide but also a mixture of two or more ofthe polyamides may be used.

The polyester which is used in the present invention is a thermoplasticpolyester having an ester linkage in the molecule, and a polyesterhaving a structure formed by polycondensation of a dicarboxylic acidwith a glycol is preferred. Polyesters of this type are obtained bypolycondensing a dicarboxylic acid or a lower ester, acid halide or acidanhydride thereof with a glycol. As the starting aromatic or aliphaticdicarboxylic acid, there are preferably used oxalic acid, malonic acid,succinic acid, glutaric acid, pimelic acid, suberic acid, adipic acid,sebacic acid, azelaic acid, 1,9-nonane-dicarboxylic acid,1,10-decane-dicarboxylic acid, 1,16-hexadecanedicarboxylic acid,terephthalic acid, isophthalic acid, p,p'-dicarboxydiphenyl,p-carboxyphenoxyacetic acid and 2,6-naphthalene-dicarboxylic acid.Mixtures of two or more of these dicarboxylic acids may also be used. Ofthe above-mentioned dicarboxylic acids, terephthalic acid andisophthalic acid are particularly preferred. An aliphatic or aromaticglycol (or diol) is used as the other starting material of thepolyester. For example, there can be mentioned ethylene glycol,1,3-propane diol, 1,2-propane diol, 1,4-butane diol, 1,6-hexane diol,1,4-cyclohexane diol, 1,10-decane diol, neopentyl glycol and p-xyleneglycol. These glycols may be used singly or in the form of a mixture oftwo or more of them. Of these glycols, alkylene glycols having 2 to 10carbon atoms are preferred, and ethylene glycol and 1,4-butane diol areparticularly preferred. Particularly valuable polyesters produced bypolycondensation of the dicarboxylic acid with the glycol arepolyethylene terephthalate and polybutylene terephthalate, and modifiedproducts thereof in which the monomer units are partly substituted withother monomer units.

From the standpoint of processability and mechanical strength of thecomposition, the number average molecular weight of the polyester isgenerally 500 to 100,000 and preferably 5,000 to 50,000.

The polymerization method for formation of the polyester used in thepresent invention is not particularly critical, and the polymerizationmay be carried out according to customary procedures. For example, theremay be mentioned a method in which the above-mentioned acid component,for example, terephthalic acid, isophthalic acid, an aliphaticdicarboxylic acid or an ester thereof is subjected to directesterification or ester exchange reaction with at least one memberselected from the above-mentioned glycols at a time or stepwise andpolymerization is then conducted. Catalysts, stabilizers, modifiers andadditives customarily used may optionally be added.

Another valuable polyester which may be used in the present invention isa polylactone obtained by ring-opening polymerization of a cycliclactone such as pivalolactone, β-propiolactone or ε-caprolactone.

The above-mentioned polyesters have hydroxyl or carboxyl groups at theterminal ends of the molecule, and these terminal functional groups maybe rendered unreactive by reaction with a monofunctional alcohol orcarboxylic acid. It is preferred that all or part of the terminal endsof the molecule of the polyester have functional groups capable ofreacting with the functional groups of the modified block copolymer. Thepolyester having these functional groups has a remarkably improvedcompatibility with the modified block copolymer because part of thesefunctional groups is reacted with the modified block copolymer.

In the present invention, the foregoing polyesters may be used alone orin combination thereof.

The thermoplastic polyester referred to in the present inventionincludes polyesters used as fibers, films or resins, such aspolyethylene terephthalate, low crystalline polyesters having a lowermelting point, and polyether-ester block copolymers containing hardsegments and soft segments in the molecule.

Thermoplastic polyurethanes which are used in the present invention aredivided into completely thermoplastic polymers and incompletelythermoplastic polymers according to synthetic conditions, that is, themolar ratio of the NCO group of the diisocyanate relative to the OHgroup of the starting bifunctional polyol or glycol. More specifically,the polyurethane synthesized in a molar ratio of about 0.95<NCO/OH≦1 isa completely thermoplastic polyurethane, and the polyurethanesynthesized in a molar ratio of about 1<NCO/OH<1.1 is an incompletelythermoplastic polyurethane. As the thermoplastic polyurethane, there maybe mentioned a polyurethane comprising a block of a polyol (polyester orpolyether) and a diisocyanate as a soft segment and a block of adiisocyanate and a glycol as a hard segment.

As the starting polyester diol, there may be mentioned poly(1,4-butyleneadipate), poly(1,6-hexane adipate) and polycaprolactone, and as thepolyether diol, there may be mentioned polyethylene glycol,polypropylene glycol and polyoxytetramethylene glycol. As the glycol,there can be mentioned ethylene glycol, 1,4-butane diol and 1,6-hexanediol. As the diisocyanate, aromatic, alicyclic and aliphaticdiisocyanates can be used. For example, there may be used tolylenediisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylenediisocyanate and isophorone diisocyanate.

Besides the foregoing thermoplastic polyurethanes, polyurethanescustomarily used as adhesives, foams or paints may be used for thecomposition of the present invention, so far as they have a sufficientcompatibility with the modified block copolymer used as the component(b) in the present invention.

From the standpoint of mechanical characteristics of the composition, itis preferred that the number average molecular weight of thethermoplastic polyurethane be 5,000 to 500,000, particularly 10,000 to300,000.

In the present invention, homopolymers of vinyl esters and olefin-vinylester copolymers, such as polyvinyl acetate, ethylene-vinyl acetatecopolymers and propylene-vinyl acetate copolymers, are preferably usedas the vinyl ester polymer.

The vinyl alcohol polymers which are used in the present inventioninclude a polymer composed of vinyl alchol units and a copolymercontaining vinyl alchol units. The polymer composed of vinyl alcholunits is a polymer obtained by partially or completely saponifying avinyl ester polymer with an aqueous alkali. In the present invention,various polyvinyl alcohols can be used. An olefin-vinyl alcoholcopolymer is preferably used as the copolymer containing vinyl alcoholunits, and from the standpoint of processability and mechanicalcharacteristics of the composition, an ethylene-vinyl alcohol copolymeris particularly preferred. The ethylene-vinyl alcohol copolymer issynthesized from the corresponding ethylene-vinyl acetate copolymer asthe starting substance. An ethylene-vinyl acetate copolymer having avinyl acetate content of 0.5 to 80 mole % is generally used, and anethylene-vinyl alcohol copolymer obtained by saponifying 10 to 100 mole% of the vinyl acetate units of this ethylene-vinyl acetate copolymer isgenerally used.

As the commercially available vinyl alcohol polymer that can be used inthe present invention, there may be mentioned EVAL manufactured and soldby Kuraray Co., Ltd., Japan and GL Resin manufactured and sold by NipponGosei Kagaku Co., Ltd., Japan.

The ionomer which is used in the present invention is an ionicallycrosslinked polymer obtained by ionically crosslinking carboxylic acidgroups in a substrate copolymer of an α,β-ethylenically unsaturatedcarboxylic acid and other monomer with at least one member selected thegroup consisting of monovalent, divalent and trivalent metal ions.

A copolymer of a non-polar monomer, for example, an olefin such asethylene, propylene or butene or styrene and an α,β-ethylenicallyunsaturated monocarboxylic acid such as acrylic acid or methacrylic acidor an α,β-ethylenically unsaturated dicarboxylic acid such as maleicacid is generally used as the substrate polymer. Anolefin-α,β-ethylenically unsaturated carboxylic acid copolymer having anolefin content of at least 50 mole % and an α,β-ethylenicallyunsaturated carboxylic acid content of 0.2 to 25 mole % is preferred.

The ionomer is prepared by reacting the above-mentioned substratepolymer, for example, an olefin-α,β-ethylenically unsaturated carboxylicacid copolymer, with a monovalent, divalent or trivalent metal compoundaccording to the process disclosed in Japanese Patent ApplicationPublication No. 6810/1964. The metal compound is added in such an amountthat 10 to 100 mole % of the carboxylic acid groups in the copolymerwill be neutralized and participate in ionic crosslinkage.

As the olefin-α,β-ethylenically unsaturated carboxylic acid, there maybe mentioned, for example, an ethylene-acrylic acid copolymer, anethylene-methacrylic acid copolymer, an ethylene-itaconic acidcopolymer, an ethylene-maleic acid copolymer, an ethylene-acrylicacid-methacrylic acid copolymer and an ethylene-propylene-methacrylicacid copolymer. Of the above-mentioned copolymers, a copolymercomprising an unsaturated monocarboxylic acid, for example, anethylene-acrylic acid copolymer or an ethylene-methacrylic acidcopolymer, is preferred.

Monovalent, divalent and trivalent ions of metals of the Groups I, II,III, IV-A and VII of the Periodic Table are used as the metal ion forthe production of the ionomer. For example, there may be mentionedmonovalent ions such as Na⁺, Li⁺, K⁺, Cs⁺ and Ag⁺, divalent ions such asMg²⁺, Ca²⁺, Ba²⁺, Zn²⁺, Sr²⁺, Hg²⁺ and Fe²⁺, and trivalent ions such asAl³⁺, and Fe³⁺. These metal ions are reacted with the substrate polymersin the form of hydroxides, alcoholates and low carboxylic acid salts.

The ionomer can also be prepared by saponifying anolefin-α,β-ethylenically unsaturated carboxylic acid ester copolymer,for example, an ethylene-methyl methacrylate copolymer or anethylene-methyl acrylate copolymer, with a hydroxide of a monovalent,divalent or trivalent metal or partially neutralizing the resultingsaponification product to convert part of the saponification product toa corresponding carboxylic acid. The so-prepared ionomer may be used asthe component (a) of the composition of the present invention.

As the commercailly available ionomer which can be used as the component(a) of the composition of the present invention, there may be mentioned"Surlyn" (the trade name of an ionomer manufactured and sold by Du PontCo., U.S.A.), "Copolene" (the trade name of an ionomer manufactured andsold by Asahi-Dow Co., Ltd., Japan) and "Hi-Milan" (the trade name of anionomer manufactured and sold by Mitsui Polychemical Co., Ltd., Japan).

The thermoplastic polymers which may be used as the component (a) of themodified block copolymer composition, other than the above-mentionedpolar thermoplastic polymers, will now be described in detail.

As the polyoxymethylene which is used in the present invention, theremay be mentioned a homopolymer obtained by polymerization offormaldehyde or trioxane or a copolymer comprising the above-mentionedmonomer as the main component. The terminal groups of the homopolymerare generally converted to ester or ether groups to improve the heatresistance or chemical resistance. As the copolymer, there may bementioned a copolymer of formaldehyde or trioxane with an aldehyde, acyclic ether, a cyclic carbonate, an epoxide, an isocyanate or a vinylcompound.

An aromatic polycarbonate having a structural unit represented by thefollowing general formula: ##STR1## wherein Ar¹ and Ar^(1') stand for aphenylene group or a phenylene group substituted with an alkyl group, asubstituted alkyl group, an alkoxy group, a halogen atom or a nitrogroup, and A stands for an alkylene group, an alkylidene group, acycloalkylene group, a cycloalkylidene group, a sulfur atom, an oxygenatom, a sulfoxide group or a sulfone group, is preferably used as thepolycarbonate in the present invention.Poly-4,4'-dioxydiphenyl-2,2'-propane carbonate is particularlypreferred.

A thermoplastic polysulfone having a structural unit represented by thefollowing general formula:

    --Ar.sup.2 --B--Ar.sup.2 --So.sub.2 -- or --Ar.sup.2' --SO.sub.2 --

wherein Ar² and Ar^(2') stand for a phenylene group, and B stands for anoxygen atom, a sulfur atom or an aromatic diol residue, is preferred asthe polysulfone that is used in the present invention. Poly(ethersulfone) and poly(4,4-bisphenol ether sulfone) are particularlypreferred.

Thermoplastic homopolymers and copolymers synthesized by using at least50% by weight of an α,β-olefinically unsaturated mononitrile as theconstituent monomer are preferably used as the nitrile polymer in thepresent invention. As the α,β-olefinically unsaturated mononitrile,there may be mentioned, for example, acrylonitrile, methacrylonitrileand α-bromoacrylonitrile. A mixture of two or more of these monomers maybe used. As the monomer to be copolymrized with the α,β-olefinicallyunsaturated mononitrile, there may be mentioned lower α-olefins such asethylene, propylene, isobutylene, pentene-1, vinyl chloride andvinylidene chloride; monovinyl substituted aromatic hydrocarbons such asstyrene, α-methylstyrene, vinyltoluene, chlorostyrene and methylstyrene;vinyl esters such as vinyl acetate; lower alkyl esters ofα,β-olefinically unsaturated carboxylic acids such as methyl acrylateand methyl methacrylate; and vinyl ethers such as vinyl methyl ether.

A polyphenylene ether having a structural unit represented by thefollowing general formula: ##STR2## wherein R¹ and R² stand for anunsubstituted or substituted alkyl group having 1 to 4 carbon atom or ahalogen atom, or a polyphenylene ether graft copolymer obtained forgrafting a styrene type compound onto the above polyphenylene ether ispreferably used as the polyphenylene ether in the present invention. Asthe styrene type compound used for the graft modification, there can bementioned styrene, α-methylstyrene, methylstyrene, tert-butylstyrene andchlorostyrene. Two or more of these styrene type compounds may be usedfor the graft polymerization. If desired, other copolymerizable vinylcompounds such as acrylic acid esters, methacrylic acid esters,acrylonitrile and methacrylonitrile may be grafted together with thestyrene type compound. Poly(2,6-dimethyl-1,4-phenylene) ether and astyrene-grafted copolymer thereof are particularly preferred as thepolyphenylene ether.

Arylene sulfide homopolymers and copolymers having a structural unitrepresented by the following general formula:

    --Ar.sup.3 --S--

wherein Ar³ stands for a phenylene group or a phenylene groupsubstituted with an alkyl group or a substituted alkyl group, arepreferably used as the polyarylene sulfide in the present invention.Polyphenylene sulfide and poly-4,4'-diphenylene sulfide are particularlypreferred.

It is preferred that the modified polycarbonate, modified polysulfone,modified polyphenylene ether and modified polyarylene sulfide which isused in the present invention be respectively a blend of theabove-mentioned polycarbonate, polysulfone, polyphenylene ether andpolyarylene sulfide with an alkenyl aromatic hydrocarbon homopolymerand/or an alkenyl aromatic hydrocarbon copolymer as the modifyingpolymer. As the alkenyl aromatic hydrocarbon homopolymer or alkenylaromatic hydrocarbon copolymer which is used for the modification, theremay be mentioned polymers containing at least 50% by weight of amonovinyl substituted aromatic hydrocarbon, for example, polystyrene, astyrene-α-methylstyrene copolymer, a butadiene-styrene block copolymer,an impact-resistant rubber-modified styrene polymer, anacrylonitrile-styrene copolymer, a styrene-methacrylic acid estercopolymer, a styrene-maleic anhydride copolymer, anacrylonitrile-butadiene-styrene copolymer, an acrylic acidester-butadiene-styrene copolymer, a methacrylic acidester-butadiene-styrene copolymer and mixtures of two or more of theforegoing polymers. From the standpoint of modification effect, it ispreferred that the content of the modifying polymer in the blend be 10to 70% by weight, particularly 20 to 50% by weight.

The modified block copolymer which is used as the component (b) of thecomposition of the present invention is at least one modified blockcopolymer comprising a block copolymer (hereinafter referred to as "baseblock copolymer") having at least one monovinyl substituted aromatichydrocarbon polymer block A and at least one olefin compound polymerblock B having an ethylenic unsaturation degree not exceeding 20%, thebase block copolymer having at least one molecular unit graftedthereonto, with the at least one molecular unit containing at least onemember selected from a carboxylic acid group and a group derivedtherefrom. The olefin compound polymer block is preferably a polymerblock in which at least one olefin compound selected from mono-olefinssuch as ethylene, propylene, 1-butene and isobutylene, conjugateddiolefins such as butadiene, isoprene and 1,3-pentadiene andnon-conjugated diolefins such as 1,4-hexadiene, norbornene andnorbornene derivatives is homopolymerized or copolymerized, and theethylenic unsaturation degree of this block does not exceed 20%. Theterm "ethylenic unsaturation degree" as used herein is intended to meanthe percent of the number of the monomer units having an unsaturatedbond relative to the number of all the monomer units constituting theolefin compound polymer block. Accordinly, the term "ethylenicunsaturation degree not exceeding 20%" as used herein is intended tomean that the percent of the number of the monomer units having anunsaturated bond relative to the number of all the monomer unitsconstituting the olefin compound polymer block does not exceed 20%. Itis preferred that the ethylenic unsaturation degree of the olefincompound polymer block be not more than 15%. If the olefin compoundpolymer block has an ethylenic unsaturation degree exceeding 20%, theweatherability and resistance to thermal deterioration of thecomposition are degraded, and no good results can be obtained.Accordingly, if a diolefin such as mentioned above is used as theconstituent monomer of the olefin compound polymer block, it isnecessary that the ethylenic unsaturation degree should be reduced byhydrogenation or the like to such an extent that the ethylenicunsaturation degree of the olefin compound polymer block does not exceed20%, preferably not more than 15%. A monovinyl substituted aromatichydrocarbon may be random-copolymerized to the olefin compound polymerblock. As the base block copolymer, there may be mentioned ahydrogenation product of a block copolymer of a monovinyl substitutedaromatic hydrocarbon and a conjugated diene compound, and a blockcopolymer of a monovinyl substituted aromatic hydrocarbon and amono-olefin. A modified block copolymer which is preferably used in thepresent invention is one prepared by addition-reacting theabove-mentioned base block copolymer with at least one modifier selectedfrom unsaturated carboxylic acids and derivatives thereof. A modifiedblock copolymer which is most preferably used in the present inventionis a modified block copolymer obtained by selectively hydrogenating ablock copolymer (hereinafter referred to as "precursory blockcopolymer") comprising at least one monovinyl substituted aromatichydrocarbon polymer block and at least one polymer block composed mainlyof a conjugated diene compound at its conjugated diene compound moietyso that the ethylenic unsaturation degree of the polymer block composedmainly of the conjugated diene compound does not exceed 20%, andaddition-reacting the hydrogenated block copolymer with at least onemodifier selected from unsaturated carboxylic acids and derivativesthereof. A precursory block copolymer comprising at least two monovinylsubstituted aromatic hydrocarbon polymer blocks and at least one polymerblock composed mainly of a conjugated diene compound is especiallypreferred. In the polymer block composed mainly of a conjugated dienecompound, it is preferred that the monovinyl substituted aromatichydrocarbon/conjugated diene compound weight ratio be in the range offrom 0/100 to 50/50, particularly from 0/100 to 30/70. In the case wherethe conjugated diene compound is copolymerized with the monovinylsubstituted aromatic hydrocarbon in this polymer block, the distributionof the monovinyl substituted aromatic hydrocarbon may be a randomdistribution, a tapering distribution (the monomer content increases ordecreases along the molecule chain), a partially blocked distribution orany combination thereof. In the precursory block copolymer of thepresent invention, a portion of a copolymer of the monovinyl substitutedaromatic hydrocarbon and the conjugated diene compound having amonovinyl substituted aromatic hydrocarbon content higher than 50% byweight may be present in the transitional portion between the monovinylsubstituted aromatic hydrocarbon polymer block and the polymer blockcomposed mainly of the conjugated diene compound. In the presentinvention, this copolymer portion is included in the polymer blockcomposed mainly of the conjugated diene compound.

In the precursory block copolymer, the monovinyl substituted aromatichydrocarbon content is 5 to 95% by weight, preferably 10 to 90% byweight, more preferably 15 to 85% by weight. When the monovinylsubstituted aromatic hydrocarbon content is not more than 60% by weight,preferably not more than 55% by weight, the precursory block copolymerhas characteristics as a thermoplastic elastomer, and when the monovinylsubstituted aromatic hydrocarbon content is more than 60%, preferablymore than 70%, the precursory block copolymer has characteristics as aresinous polymer.

At least one member selected from styrene, α-methylstyrene,o-methylstyrene, m-methylstyrene, p-methylstyrene, dimethylstyrene andp-tert-butylstyrene is preferably used as the monovinyl substitutedaromatic hydrocarbon constituting the precursory block copolymer, andstyrene is particularly preferred. At least one member selected frombutadiene, isoprene and 1,3-pentadiene is preferably used as theconjugated diene compound, and butadiene and/or isoprene is particularlypreferred. The number average molecular weight of the precursory blockcopolymer is 20,000 to 500,000, preferably 40,000 to 300,000. It ispreferred that the ratio of the weight average molecular weight relativeto the number average molecular weight be in the range of from 1.05 to10. The weight average molecular weight can be measured by theultra-centrifugal method and the number average molecular weight can bemeasured by the osmotic pressure method. In the precursory polymerblock, it is preferred that the vinyl content of the conjugated dieneportion be 10 to 80%. When it is necessary that rubbery elasticityshould be given to the modified block copolymer, it is preferred thatthe vinyl content be 25 to 65%, particularly 35 to 55%. The vinylcontent of the precursory block copolymer can be measured by means of anuclear magnetic resonance apparatus.

When the precursory block copolymer contains at least two monovinylsubstituted aromatic hydrocarbon polymer blocks or at least two polymerblocks composed mainly of the conjugated diene, these blocks may havethe same structure, or they may be different in monomer content, monomerdistribution in the molecule chain, molecular weight of the block andlinking manner of the conjugated diene portion.

As the method for preparing the precursory block copolymer, there may bementioned methods disclosed in British Patent No. 895,980, BritishPatent No. 1,130,770, U.S. Pat. No. 3,281,383, Japanese PatentApplication Publication No. 2423/1973 and U.S. Pat. No. 3,639,517.According to each of these methods, the monovinyl substituted aromatichydrocarbon is block-copolymerized with the conjugated diene compound ina hydrocarbon solvent using as an anion polymerization initiator anorganic lithium compound or the like and if necessary using as a vinylmodifier an ether compound such as diethyl ether or tetrahydrofuran, atertiary amine such as triethyl amine or N,N,N',N'-tetramethylethylenediamine or a Lewis base such as a phosphine compound, e.g.,hexamethylphosphamide, and as a coupling agent a polyfunctional compoundsuch as silicon tetrachloride or epoxidized soy bean oil. A blockcopolymer having a linear, branched or radial structure can be obtained.In the present invention, a block copolymer prepared according to any ofthe foregoing polymerization methods can be used. Not only oneprecursory block copolymer but also a mixture of two or more precursoryblock copolymers may be used.

The base block copolymer can be obtained by hydrogenating theabove-mentioned precursory block copolymer according to a known method,for example, the method disclosed in British Patent No. 1,020,720. It isrequisite that at least 80%, preferably at least 85%, of the monomerunits having an aliphatic double bond in the polymer block composedmainly of the conjugated diene compound in the precursory blockcopolymer should be hydrogenated. In other words, it is requisite thatthe ethylenic unsaturation degree of the olefin compound polymer block Bformed by conversion of the polymer block composed mainly of theconjugated diene compound by hydrogenation should not exceed 20%,preferably not exceed 15%. As pointed out hereinbefore, if the ethylenicunsaturation degree of the olefin compound polymer block exceeds 20%,the weatherability or resistance to thermal deterioration of thecomposition is degraded and good results can not be obtained. From thestandpoint of mechanical characteristics, it is preferred that thedegree of hydrogenation of the monomer units containing aromatic doublebonds derived from the monovinyl substituted aromatic hydrocarbon in themonovinyl substituted aromatic hydrocarbon polymer block and themonovinyl substituted aromatic hydrocarbon copolymerized according toneed to the polymer block composed mainly of the conjugated dienecompound be not more than 20%. The ethylenic unsaturation degree of theolefin compound polymer block can be measured by instrumental analysisusing an infrared spectrophotometer (IR) or a nuclear magnetic resonanceapparatus (NMR) or by titration analysis such as iodine titration.

The base block copolymer is then modified by addition reaction with atleast one modifier selected from unsaturated carboxylic acids andderivatives thereof, whereby a modified block copolymer to be used inthe present invention is obtained. As the unsaturated carboxylic acid orits derivative which is used as the modifier, there may be mentioned,for example, maleic acid, maleic anhydride, maleic acid esters, maleicacid amides, maleic acid imides, fumaric acid, fumaric acid esters,fumaric acid amides, fumaric acid imides, itaconic acid, itaconicanhydride, itaconic acid esters, itaconic acid amides, itaconic acidimides, halogenated maleic acid, halogenated maleic anhydride,halogenated maleic acid esters, halogenated maleic acid amides,halogenated maleic acid imides, cis-4-cyclohexene-1,2-dicarboxylic acid,cis-4-cyclohexene-1,2-dicarboxylic anhydride,cis-4-cyclohexene-1,2-dicarboxylic acid esters,cis-4-cyclohexene-1,2-dicarboxylic acid amides,cis-4-cyclohexene-1,2-dicarboxylic acid imides,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid esters,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid amide,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid imide, acrylicacid, acrylic acid esters, acrylic acid amide, methacrylic acid,methacrylic acid esters and methacrylic acid amide. These modifiers maybe used alone or in combination thereof. Among these modifiers,unsaturated dicarboxylic acids and derivatives thereof are preferred andmaleic anhydride is particularly preferred.

The modified block copolymer is obtained by grafting the above-mentionedmodifier onto the base block polymer in a solution state or molten statein the presence or absence of a radical initiator. The method forpreparing the modified block copolymer is not particularly critical inthe present invention. However, a method providing a modified blockcopolymer containing an undesirable component such as gel or a modifiedblock copolymer having an extremely high melt viscosity and degradingthe processability of the composition is not preferred. For example,there is preferably adopted a method in which the base block copolymeris reacted with the above-mentioned modifier in the presence of aradical initiator in, for example, an extruder.

The amount of the molecular unit containing a carboxylic acid group or agroup derived therefrom, which is contained in the modified blockcopolymer, that is, the amount of the unsaturated carboxylic acid or itsderivative grafted onto the base block copolymer, is 0.05 to 30 parts byweight, preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10parts by weight, per 100 parts by weight of the base block copolymer, asthe mean value in the entire modified block copolymer used in thepresent invention. When this amount of the molecular unit containing acarboxylic acid group or a group derived therefrom is smaller than 0.05part by weight, no significant modification effect can be obtained overthe unmodified block copolymer, and even if this amount exceeds 30 partsby weight, no substantial increase of the modification effect can beattained.

The content of the molecular unit containing a carboxylic acid group ora group derived therefrom in the modified block copolymer can be easilydetermined by infrared spectrophotometry or titration. In the presentinvention, the unmodified block copolymer may be contained in themodified block copolymer used as the component (b), so far as the amountof the unsaturated carboxylic acid or its derivative grafted onto thebase block copolymer as the mean value in the entire component (b) is inthe above-mentioned range.

In the present invention, the modified block copolymer may be anionically crosslinked modified block copolymer. This ionicallycrosslinked modified block copolymer is obtained by crosslinking theabove-mentioned modified block copolymer through at least one memberselected from monovalent, divalent and trivalent metal ions. Namely, thecrosslinked modified block copolymer is prepared by reacting themodified block copolymer with at least one crosslinking agent selectedfrom monovalent, divalent and trivalent metal compounds.

In the ionically crosslinked modified block copolymer, the carboxylicacid group and/or the group derived therefrom of the modified blockcopolymer is ionized by addition of the above-mentioned crosslinkingagent. The degree of ionization can be adjusted according to the amountof the crosslinking compound employed, and the degree of ionization canbe determined by, for example, an infrared spectrophotometer.

The crosslinking agent is added in such an amount that a carboxylic acidgroup and/or a group derived therefrom, which is contained in themodified block copolymer, is partially or completely ionized. Theionization reaction is advanced substantially quantitatively, but insome case, in order to obtain the desirable degree of ionization, it isnecessary to add the crosslinking agent in excess of thestoichiometrical amount. In order to obtain the ionically crosslinkedmodified block copolymer effectively, it is preferred that the ratio ofthe mole number of the metal compound relative to the total mole numberof the carboxylic acid group and the group derived therefrom, containedin the modified block copolymer be in the range of from 0.1 to 3.0.

At least one member selected from compounds of metals of the Groups I,II and III of the Periodic Table is preferably used as the crosslinkingagent to be added to the modified block copolymer for formation of theionically crosslinked modified block copolymer. More specifically atleast one member selected from lithium compounds, sodium compounds,potassium compounds, magnesium compounds, calcium compounds, zinccompounds and aluminum compounds is preferably used. It is preferredthat these compounds are hydroxides, alcoholates or carboxylic acidsalts.

As the method for obtaining the ionically crosslinked modified blockcopolymer, there may be mentioned a method in which the crosslinkingagent is added to the melt of the modified block copolymer, a method inwhich the modified block copolymer is dissolved in an appropriatesolvent, for example, an organic solvent such as toluene, benzene ortetrahydroruran and the crosslinking agent is added to the solution toeffect the crosslinking reaction, and a method in which the crosslinkingagent is added to a latex of the modified block copolymer. Any of thesemethods can be used for formation of the ionically crosslinked modifiedblock copolymer to be used in the present invention.

The ionically crosslinked modified block copolymer which is used in thepresent invention is thermoplastic, and a composition obtained by mixingthis modified block copolymer with the component (a) is processable athigh temperatures, and the ionic crosslinkage is a reversiblecrosslinkage. These characteristic properties are not possessed by blockcopolymers obtained through irreversible crosslinkage such as sulfurcrosslinkage, peroxide crosslinkage or irradiation crosslinkage.

The composition of the present invention includes an ionicallycrosslinked composition obtained by adding the crosslinkage agent to amixture of the thermoplastic polymer as the component (a) and themodified block copolymer as the component (b) which is molten ordissolved in an appropriate solution, to effect the crosslinkingreaction.

From the standpoint of mechanical characteristics of the composition, itis preferred that the monovinyl substituted aromatic hydrocarbon contentof the base block copolymer of the component (b) of the modified blockcopolymer composition of the present invention be 5 to 95% by weight.When the modified block copolymer as the component (b) is required tohave a rubbery elasticity, it is preferred that the monovinylsubstituted aromatic hydrocarbon content of the base block copolymer be5 to 60% by weight. On the other hand, when the modified block copolymeras the component (b) is required to have resinous characteristics, it ispreferred that the monovinyl substituted aromatic hydrocarbon content ofthe base block copolymer be over 60% by weight up to 95% inclusive byweight. As pointed out hereinbefore, the modified block copolymercomposition of the present invention can be a resinous composition, arubbery composition or a leather-like composition according to the ratioof the thermoplastic polymer as the component (a) relative to themodified block copolymer as the component (b) and the monovinylsubstituted aromatic hydrocarbon content of the base block copolymer ofthe modified block copolymer as the component (b). In the case where aresinous composition is obtained, when the monovinyl substitutedaromatic hydrocarbon content of the base block copolymer is over 60% byweight up to 95% inclusive by weight, preferably 65 to 90% by weight,the component (a)/component (b) weight ratio is adjusted in the range offrom 90/10 to 5/95, preferably from 85/15 to 10/90, more preferably from80/20 to 15/85, and when the monovinyl substituted aromatic hydrocarboncontent of the base block copolymer is 5 to 60% by weight, preferably 10to 55% by weight, more preferably 15 to 50% by weight, the component(a)/component (b) weight ratio is adjusted in the range of from over50/50 up to 98/2 inclusive, preferably from 60/40 to 95/5, morepreferably from 70/30 to 90/10. When the amount of the component (b) istoo small and below the above range, no substantial effect of improvingthe impact resistance or paint adhesion can be attained, and when theamount of the component (b) is too large, the rigidity is degraded. Inthe case where a rubbery or leather-like composition is prepared, whenthe monovinyl substituted aromatic hydrocarbon content of the base blockcopolymer is 5 to 60% by weight, preferably 10 to 55% by weight, morepreferably 15 to 55% by weight, the component (a)/component (b) weightratio is adjusted in the range of from 2/98 to 50/50, preferably 5/95 to40/60, more preferably from 10/90 to 30/70. When the amount of thecomponent (a) is too small and below the above range, no substantialimprovement of the composition as a rubbery or leather-like compositioncan be attained. When the amount of the component (a) is too large, therubbery or leather-like characteristics are lost and the compositionbecomes resinous.

Reinforcers, fillers, antioxidants, ultraviolet absorbers, coloringagents, pigments, lubricants, flame retardants, foaming agents and otheradditives may be added to the modified block copolymer composition ofthe present invention. Specific examples of the additives which can beadded to the composition of the present invention are described in"Handbook of Additive Chemicals to Rubbers and Plastics" published byRubber Digest Co., Ltd, Japan in 1974.

For example, a composition obtained by adding 5 to 150 parts by weight,preferably 10 to 100 parts by weight, of a glass fiber to 100 parts byweight of the resinous modified block copolymer composition of thepresent invention is an excellent molding material having improvedrigidity, heat resistance and mechanical strength. Glass fibers having adiameter of 2 to 20μ and a length of 50 to 20,000μ, customarilyincorporated into resins, are preferably used.

When the rubbery or leather-like modified block copolymer composition ofthe present invention is used as a material for a shoe sole or anindustrial article, a finely divided solid such as calcium carbonate,clay, silica or titanium dioxide may be added as a filler or pigment,and a hardness adjusting agent, for example, a resin such as polystyreneor polyolefin and a moldability adjusting agent, for example, a processoil such as a paraffin oil or a naphthene oil may be added according toneed. An Example of the amounts of these additive added to the modifiedblock copolymer composition are as follows:

Rubbery or leather-like composition of the present invention: 100 partsby weight

Resin: 30 to 100 parts by weight

Process oil: 50 to 100 parts by weight

Finely divided filler: 20 to 200 parts by weight

The modified block copolymer composition of the present invention may beformed by mixing the components (a) and (b) by means of a mixing deviceappropriately selected according to the mixing ratio of the components(a) and (b) from various mixing devices such as a single screw extruder,a multiple screw extruder, a mixing roll, a Banbury mixer and a kneader.It is preferred that the mixing be carried out in the molten state.Moreover, the composition of the present invention can be formedaccording to a method in which the respective components are dissolvedin an organic solvent such as toluene, benzene or tetrahydrofuran andthe solvent is removed from the resulting mixture by heating.

The modified block copolymer composition of the present invention can beeasily molded into various, practically valuable products such assheets, foams, films and injection molded, blow molded, pressure formedand rotary molded articles having various shapes according to optionalknown molding methods such as extrusion molding, injection molding, blowmolding and rotary molding methods.

The so-obtained molded articles formed of the modified block copolymerof the present invention may be painted or plated according to need. Anyof known paints such as acrylic resin paints, vinyl-modified acrylicresin paints, alkyd resin paints, polyurethane resin paints, epoxy resinpaints, phenolic resin paints, melamine resin paints and urea resinpaints may be used for painting these molded articles.

A metallic feel can be imparted to the molded articles by a platingtreatment. Any of the known plating methods such as chemical plating andelectrical plating methods may be adopted. In case of the resinousmodified block copolymer composition of the present invention comprisingthe ionically crosslinked modified block copolymer as the compoennt (b),when the incorporated amount of the component (a) is relatively large,the component (b) is dispersed in the component (a) in the peculiar formdifferent from the circular or oval form observed in conventionaldifferent polymer mixtures, and therefore, when a molded article of thiscomposition is chemically etched and then plated, a high anchor effectcan be attained and a plated molded article having a high plate adhesioncan be obtained.

PREFERRED EMBODIMENTS OF THE INVENTION

The present invention will now be described in more detail withreference to the following Examples.

In the Examples, the number average molecular weights of polymers weredetermined according to the osmotic pressure method and the weightaverage molecular weights were determined according to theultra-centrifugal method. Furthermore, the melt index values referred toin the Examples are those determined according to the method of ASTMD-1238.

(1) Preparation of Unmodified Block Copolymers

Unmodified block copolymers shown in Table 1 were prepared by subjectingbutadiene and styrene to anionic block copolymerization in n-hexane orcyclohexane as a solvent by using n-butyl lithium as a polymerizationcatalyst and tetrahydrofuran as a vinyl content adjusting agent. Forexample, an unmodified block copolymer A-1 was prepared by performingpolymerization according to the following procedures. To an n-hexanesolution containing 13 parts by weight of butadiene (butadieneconcentration, 20% by weight) were added 0.1 part by weight of n-butyllithium and 5 parts by weight of tetrahydrofuran, and polymerization wascarried out at about 60° C. for 1 hour. After substantial completion ofthe polymerization of butadiene, an n-hexane solution containing 20parts by weight of styrene (styrene concentration, 20% by weight) wasadded to the resulting reaction mixture and polymerization was carriedout at about 60° C. for 1 hour. After substantial completion of thepolymerization of styrene, an n-hexane solution containing 47 parts byweight of butadiene (butadiene concentration, 20% by weight) was addedto the resulting reaction mixture and polymerization was carried out atabout 60° C. for 1 hour. After substantial completion of thepolymerization of butadiene, an n-hexane solution containing 20 parts byweight of styrene (styrene concentration, 20% by weight) was added tothe resulting reaction mixture and polymerization was carried out atabout 60° C. for 1 hour to obtain the unmodified block copolymer A-1.

When unmodified block copolymers A-4 and A-5 were prepared, silicontetrachloride was used as a coupling agent.

2,6-Di-tert-butyl-4-methylphenol (hereinafter often referred to as"BHT") was added as a stabilizer to each of the unmodified blockcopolymers shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Unmodified            Vinyl Content*.sup.2                                                                  Number Aver-                                    Block Polymer                                                                              Styrene Content                                                                        (%) in Buta-                                                                          age Molecu-                                     Copolymer                                                                           Structure                                                                            % by weight)                                                                           diene Block                                                                           lar Weight                                      __________________________________________________________________________    A-1   B--S--E--S                                                                           40       42       64,000                                         A-2                            55,000                                         A-3   S--B--S                                                                              30       38       75,000                                         A-4   Si(B--S).sub.4                                                                       30       48      164,000                                         A-5   Si(B--S).sub.4                                                                       70       53      105,000                                         A-6   S--B'--S                                                                             80       36      120,000                                         __________________________________________________________________________     Note:                                                                         *.sup.1 B stands for a butadiene polymer block, B'stands for a                butadienestyrene random compolymer block, and S stands for a styrene          polymer block.                                                                *.sup.2 The vinyl content was measured using a nuclear magnetic resonance     apparatus.                                                               

(2) Preparation of Hydrogenated Block Copolymers

The unmodified block copolymer shown in Table 1 was put in ann-hexane/cyclohexane mixed solvent or a cyclohexane solvent, andhydrogenation was carried out at 50° C. under a hydrogen pressure of 7Kg/cm² for 5 hours using cobalt naphthenate and triethyl aluminum ascatalysts, whereby there was obtained a selectively hydrogenated blockcopolymer in which about 90% of double bonds of the butadiene block werehydrogenated but benzene rings of the styrene block were scarcelyhydrogenated. The metals of the catalyst residue were removed by washingwith an aqueous solution of hydrochloric acid and methanol.

The hydrogenated block copolymers obtained by thus hydrogenating theunmodified block copolymers A-1 through A-6 shown in Table 1 aredesignated as hydrogenated block copolymers B-1 through B-6,respectively.

(3) Preparation of Modified Hydrogenated Block Copolymers

To 100 parts by weight of the so-obtained hydrogenated block copolymerwas added 1 to 5 parts by weight of maleic anhydride so that a desiredamount of maleic anhydride was added to the hydrogenated blockcopolymer, and 0.1 part by weight of Perhexa 25B [the trade name of2,5-dimethyl-2,5-di(t-butylperoxy)hexane manufactured and sold by NipponYushi K.K., Japan] was added to the mixture, and the mixture washomogeneously blended and supplied to a single screw extruder having adiameter of 20 mm [length/diameter ratio (hereinafter often referred toas "L/D")=24]. The maleinization reaction was carried out at a cylindertemperature of 250° C. to prepare a modified copolymer. Unreacted maleicanhydride was removed from the modified hydrogenated block copolymer byheating under reduced pressure, and BHT was added as a stabilizer in anamount of 0.5 part by weight per 100 parts by weight of the modifiedcopolymer. Thus, modified hydrogenated block copolymers shown in Table 2were prepared. The analysis values of the obtained modified hydrogenatedblock copolymer are shown in Table 2. The modified hydrogenated blockcopolymers obtained by hydrogenating and modifying the unmodified blockcopolymers A-1, A-2, A-4, A-5 and A-6 shown in Table 1 are designated asmodified hydrogenated block copolymers C-1, C-2, C-5, C-6 and C-7,respectively. The modified hydrogenated block copolymers obtained byhydrogenating the unmodified block copolymer A-3 and modifying thehydrogenated block copolymer so that the amounts of maleic anhydridegrafted onto the hydrogenated block copolymer were 1.2% by weight and0.7% by weight are designated as modified hydrogenated block copolymersC-3 and C-4, respectively.

                  TABLE 2                                                         ______________________________________                                                           Amount of Maleic                                                              Anhydride*.sup.3                                                                            Tolune-                                      Modified  Polymer  Grafted onto  Insoluble                                    Hydrogenated                                                                            before   Hydrogenated  Component                                    Block     Hydro-   Block Copolymer                                                                             Content                                      Copolymer genation (% by weight) (% by weight)                                ______________________________________                                        C-1       A-1      1.4           0.04                                         C-2       A-2      1.8           0.04                                         C-3       A-3      1.2           0.04                                         C-4                0.7           0.05                                         C-5       A-4      2.3           0.05                                         C-6       A-5      1.2           0.02                                         C-7       A-6      0.5           0.01                                         ______________________________________                                         Note:                                                                         *.sup.3 The amount of maleic anhydride grafted onto the hydrogenated bloc     copolymer was measured by the neutralization titration method using sodiu     methylate.                                                               

(4) Preparation of Modified Unhydrogenated Block Copolymers

Modified unhydrogenated block copolymers D-1, D-2, and D-3 were preparedby grafting maleic anhydride onto the unmodified block copolymers A-2,A-3 and A-5 according to the following procedures.

To 100 parts by weight of the unmodified block copolymer was added 2 to5 parts by weight of maleic anhydride so that a desired amount of maleicanhydride was grafted onto the unmodified block copolymer, and 0.3 partby weight of BHT and 0.2 part by weight of phenothiazine were added tothe mixture. The mixture was homogeneously blended using a mixer.

The mixture was supplied to a single extruder having a diameter of 20 mm(L/D=24) and the maleinization reaction was carried out at a cylindertemperature of 250° C. to prepare a modified copolymer. Unreacted maleicanhydride was removed from the obtained modified copolymer by dryingunder reduced pressure. Then, 0.5 part by weight of BHT was added to 100parts by weight of the modified copolymer. Thus, modified unhydrogenatedblock copolymers shown in Table 3 were prepared. The analysis values ofthe obtained modified unhydrogenated polymers are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                                  Amount of Maleic                                                              Anhydride Grafted                                   Modified                  onto Unmodified                                     Unhydrogenated                                                                              Polymer before                                                                            Block Copolymer                                     Block Copolymer                                                                             Modification                                                                              (% by weight)                                       ______________________________________                                        D-1           A-2         1.8                                                 D-2           A-3         0.7                                                 D-3           A-5         1.2                                                 ______________________________________                                    

(5) Preparation of Ionically Crosslinked Modified Block Copolymer

Ionically crosslinked modified block copolymers E-1 through E-4 wereobtained according to a recipe shown in Table 4. When the ioniccrosslinking was carried out in a solvent, the solvent was removed byheating after the crosslinking reaction. By the infrared spectrum, itwas confirmed that the acid anhydride groups in the samples E-1 throughE-4 were ionized.

                                      TABLE 4                                     __________________________________________________________________________                   Ionically Crosslinked Modified Block Copolymer                 Conditions     E-1    E-2   E-3     E-4                                       __________________________________________________________________________    Ionic Crosslinking Reaction                                                   Modified Hydrogenated                                                                        C-2    C-5   C-6     C-7                                       Block Copolymer                                                               Crosslinking                                                                         Kind    CH.sub.3 ONa                                                                         Mg(OH).sub.2                                                                        Al(OH).sub.3                                                                          KOH                                       agent  Amount (parts                                                                         0.5    0.7   0.5     0.1                                              by weight)*.sup.4                                                             Crosslinking                                                                          0.5    0.5   0.5     0.25                                             Agent/Acid                                                                    Anhydride                                                                     Molar Ratio                                                            Crosslinking   in toluene                                                                           in molten                                                                           in molten                                                                             in molten                                 Reaction Method                                                                              solution,                                                                            state, mix-                                                                         state, Bra-                                                                           state, Bra-                                              20 wt. %                                                                             ing roll,                                                                           bender  bender                                                   polymer                                                                              160° C., 15                                                                  Plasto- Plasto-                                                  concentra-                                                                           minutes                                                                             graph, 200° C.,                                                                graph,                                                   tion, room   5 minutes                                                                             200° C., 5                                        temperature, minutes                                                          1 hour                                                         __________________________________________________________________________     Note:                                                                         *.sup.4 The amount added per 100 parts by weight of the modified              hydrogenated block copolymer.                                            

EXAMPLES 1 AND 2 AND COMPARATIVE EXAMPLES 1 AND 2

A resinous composition was obtained by mixing 80 parts by weight ofnylon 6 (number average molecular weight: 18,000) as the polarthermoplastic polymer with 20 parts by weight of the modifiedhydrogenated block copolymer C-1 shown in Table 2 by means of a screwtype extruder having a diameter of 30 mm (twin, L/D=28).

Another resinous composition was obtained in the same manner asdescribed above except that the modified block copolymer C-2 was usedinstead of the modified hydrogenated block copolymer C-1.

For comparison, a comparative resinous composition was obtained in thesame manner as described above except that the unmodified blockcopolymer A-1 shown in Table 1 was used instead of the modifiedhydrogenated block copolymer C-1 or C-2.

Another comparative resinous composition was obtained in the same manneras described above except that the unmodified block copolymer A-3 wasused instead of the modified hydrogenated copolymer C-1 or C-2 or theunmodified block copolymer A-1.

Test pieces were prepared of the so-obtained resinous compositions byinjection molding, and the physical properties of the test pieces weremeasured. The obtained results are shown in Table 5.

As will be readily understood from the results shown in Table 5, thecompositions of the present invention are excellent in compatibility andhave a highly improved impact resistance over the comparativecompositions.

                  TABLE 5                                                         ______________________________________                                                                   Com-     Com-                                                                 parative parative                                             Example                                                                              Example  Example  Example                                              1      2        1        2                                         ______________________________________                                        Composition                                                                   (% by weight)                                                                 Modified hydro-                                                                            20       --       --     --                                      genated block                                                                 copolymer C-1                                                                 Modified hydro-                                                                            --       20       --     --                                      genated block                                                                 copolymer C-3                                                                 Unmodified block                                                                           --       --       20     --                                      copolymer A-1                                                                 Unmodified block                                                                           --       --       --     20                                      copolymer A-3                                                                 Nylon 6      80       80       80     80                                      Physical properties                                                           Izod impact  21.0     18.5      6.0    5.4                                    strength (Kg · cm/cm,                                                notched)*.sup.5                                                               Tensile strength                                                                           610      590      450    430                                     (yield point)                                                                 Kg/cm.sup.2)*.sup.6                                                           Elongation (%)*6                                                                           115      110      60     56                                      Transparency 13.2     14.5     56.0   58.5                                    (Haze) (%)*.sup.7                                                             ______________________________________                                         Note:                                                                         *.sup.5 The Izod impact strength was measured according to ASTM D256.         *.sup.6 The tensile strength and elongation were measured according to        ASTM D638.                                                                    *.sup.7 The transparency was measured according to JIS K6714.            

EXAMPLE 3 AND COMPARATIVE EXAMPLE 3

A rubbery composition was obtained by kneading 30 parts by weight ofnylon 6 (number average molecular weight: 18,000) as a polarthermoplastic polymer with 70 parts by weight of the modifiedhydrogenated block copolymer C-1 shown in Table 2 for 10 minutes bymeans of a Brabender Plastograph. Test pieces were prepared of theobtained composition by compression molding, and the physical propertieswere determined.

For comparison, a comparative rubbery composition was obtained in thesame manner as described above except that the unmodified blockcopolymer A-1 shown in Table 1 was used instead of the modifiedhydrogenated block copolymer C-1, and test pieces were prepared of thecomposition and the physical properties were determined.

The obtained results are shown in Table 6.

As will be readily understood from the results shown in Table 6, thecomposition of the present invention comprising the modifiedhydrogenated block copolymer and nylon 6 is highly improved incompatibility over the comparative composition, as is proved by thevalues of the transparency. Moreover, the composition of the presentinvention has high tensile strength and modulus and is improved in heatresistance represented by the tensile strength at a high temperature.Furthermore, the composition of the present invention is characterizedby a highly improved weatherability.

                  TABLE 6                                                         ______________________________________                                                                  Comparative                                                           Example 3                                                                             Example 3                                           ______________________________________                                        Composition (parts by weight)                                                 Modified hydrogenated block                                                                       70        --                                              copolymer C-1                                                                 Unmodified block copolymer A-1                                                                    --        70                                              Nylon 6             30        30                                              Physical properties                                                           25° C.                                                                       Hardness *8       94        93                                                Tensile strength *8                                                                             195       78                                                (breaking point) (Kg/cm.sup.2)                                                300% Modulus *8 (Kg/cm.sup.2)                                                                   175       70                                                Elongation *8     400       330                                         50° C.                                                                       Tensile strength *8                                                                             100       30                                                (breaking point) (Kg/cm.sup.2)                                          70° C.                                                                       Tensile strength *8                                                                             70        12                                                (breaking point) (Kg/cm.sup.2)                                          Oil resistance *9 (volume in-                                                                     23        45                                              crease ratio) (%) (oil JIS No.                                                3, 23° C., 22 hours)                                                   Transparency (Haze) (%)                                                                           15        65                                              Weatherability (%) *10 (strength                                                                  96        34                                              retention after 100 hours'                                                    exposure in weatherometer)                                                    ______________________________________                                         Note:-                                                                        *8 The hardness, tensile strength, 300% modulus and elongation were           measured according to JIS K6301.                                              *9 The oil resistance (volume increase ratio) was measured according to       JIS K6310.                                                                    *10 The weatherability was evaluated based in the elongation retention,       that is, the ratio of the elongation of the test piece after 100 hours'       exposure in the weatherometer (XWWR available from Atlas Co., U.S.A.;         light irradiation only) to the elongation of the test piece before the        exposure, and was calculated according to the following                       Elongation retention (%) (weatherability)                                     ##STR3##                                                                 

EXAMPLES 4 AND 5 AND COMPARATIVE EXAMPLES 4 AND 5

Resinous compositions were prepared in the same manner as in Examples 1and 2 and Comparative Examples 1 and 2 except that nylon 66 (numberaverage molecular weight: 20,000) was used instead of nylon 6. In thesame manner as in Examples 1 and 2 and Comparative Examples 1 and 2,test pieces were prepared of the obtained compositions and the physicalproperties were determined. The obtained results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                                   Com-     Com-                                                                 parative parative                                             Example                                                                              Example  Example  Example                                              4      5        4        5                                         ______________________________________                                        Composition                                                                   (parts by weight)                                                             Modified hydro-                                                                            20       --       --     --                                      genated block                                                                 copolymer C-1                                                                 Modified hydro-                                                                            --       20       --     --                                      genated block                                                                 copolymer C-3                                                                 Unmodified block                                                                           --       --       20     --                                      copolymer A-3                                                                 Unmodified block                                                                           --       --       --     20                                      copolymer A-3                                                                 Nylon 66     80       80       80     80                                      Physical properties                                                           Izod impact  28       24        7.6    7.0                                    strength*.sup.5 Kg · cm/cm,                                          notched)                                                                      Tensile strength*.sup.6                                                                    660      630      475    460                                     (yield point)                                                                 (Kg/cm.sup.2)                                                                 Elongation*.sup.6 (%)                                                                      54       51       45     47                                      Transparency*.sup.7                                                                        14.8     15.2     58.0   61.5                                    (Haze) (%)                                                                    ______________________________________                                         Note: *.sup.5,*.sup.6,*.sup.7 See the Note under Table 5.                

EXAMPLES 6 AND 7 AND COMPARATIVE EXAMPLES 6 AND 7

A resinous composition was obtained by mixing 80 parts by weight of PBT1041 (the trade name for polybutylene terephthalate manufactured andsold by Toray Industries Inc., Japan) as a polar thermoplastic polymerwith 20 parts by weight of the modified hydrogenated block copolymer C-1shown in Table 2 by means of a screw type extruder having a diameter of30 mm (twin, L/D=28).

Another resinous composition was obtained in the same manner asdescribed above except that the modified hydrogenated block copolymerC-3 was used instead of the modified hydrogenated block copolymer C-1.

For comparison, a comparative resinous composition was obtained in thesame manner as described above except that the unmodified blockcopolymer A-1 shown in Table 1 was used instead of the modifiedhydrogenated block copolymer C-1 or C-3.

Another comparative resinous composition was obtained in the same manneras described above except that the unmodified block copolymer A-3 wasused instead of the modified hydrogenated block copolymer C-1 or C-3 orthe unmodified block copolymer A-1.

Test pieces were prepared of the so-obtained compositions by injectionmolding, and the physical properties thereof were measured. The obtainedresults are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                                                   Com-     Com-                                                                 parative parative                                             Example                                                                              Example  Example  Example                                              6      7        6        7                                         ______________________________________                                        Composition                                                                   (parts by weight)                                                             Modified hydro-                                                                            20       --       --     --                                      genated block                                                                 copolymer C-1                                                                 Modified hydro-                                                                            --       20       --     --                                      genated block                                                                 copolymer C-3                                                                 Unmodified block                                                                           --       --       20     --                                      copolymer A-1                                                                 Unmodified block                                                                           --       --       --     20                                      copolymer A-3                                                                 Polybutylene 80       80       80     80                                      terephthalate                                                                 Physical properties                                                           Izod impact  5.2      5.6      2.4    2.3                                     strength*.sup.5                                                               (Kg · cm/cm,                                                         notched)                                                                      Tensile strength*.sup.6                                                                    514      532      505    500                                     (yield point)                                                                 (Kg/cm.sup.2)                                                                 Elongation*.sup.6 (%)                                                                      36       30       28     25                                      Heat distortion                                                                            150      152      152    150                                     temperature*.sup. 11                                                          (° C.) (under load                                                     of 4.64 Kg/cm.sup.2)                                                          ______________________________________                                         Note:                                                                         *.sup.11 The heat distortion temperature was measured according to ASTM       D648.                                                                         *.sup.5 and *.sup.6 See the Note under Table 5.                          

EXAMPLE 8 AND COMPARATIVE EXAMPLE 8

A polyester prepared from ethylene glycol (diol component), terephthalicacid (dicarboxylic acid component) and isophthalic acid (dicarboxylicacid component) and having a softening point of 195° C. and an intrinsicviscosity of 0.75 (as measured at 35° C. in o-chlorophenol) was used asa polar thermoplastic polymer.

A rubbery composition was obtained by mixing 20 parts by weight of theabove-mentioned polyester as a polar thermoplastic polymer with 80 partsby weight of the modified hydrogenated block copolymer C-1 shown inTable 2 by using a screw type extruder having a diameter of 30 mm (twin,L/D=28).

For comparison, a comparative rubbery composition was prepared in thesame manner as described above except that the unmodified blockcopolymer A-1 shown in Table 1 was used instead of the modifiedhydrogenated block copolymer C-1.

Test pieces were prepared of the so-obtained compositions by compressionmolding, and the physical properties thereof were determined. Theobtained results are shown in Table 9. ##STR4##

As will be readily understood from the results shown in Table 9, thecomposition of Example 8 comprising the modified hydrogenated blockcopolymer and the polyester is excellent over the composition ofComparative Example 8 comprising the unmodified block copolymer and thepolyester in mechanical properties such as the tensile strength and 300%modulus, the oil resistance and the heat resistance represented by thetensile strength retention at 50° C., and the composition of the presentinvention is a very valuable material.

EXAMPLES 9 THROUGH 11 AND COMPARATIVE EXAMPLES 9 AND 10

A resinous composition was obtained by mixing and kneading EVAL EP-E[the trade name for an ethylene-vinyl alcohol copolymer, obtained bysaponifying an ethylene-vinyl acetate copolymer, manufactured and soldby Kuraray Co., Ltd., Japan] with the modified hydrogenated blockcopolymer C-1 shown in Table 2 at a mixing ratio shown in Table 10 bymeans of a mixing roller.

Another resinous composition was obtained by mixing and kneading 75parts by weight of EVAL EP-E with 25 parts by weight of the modifiedhydrogenated block copolymer C-3 by means of a mixing roller.

A comparative resinous composition was obtained by mixing and kneading75 parts by weight of EVAL EP-E with 25 parts by weight of theunmodified block copolymer A-1 shown in Table 1 by means of a mixingroll.

Another comparative resinous composition was obtained in the same manneras described above except that the unmodified block copolymer A-3 shownin Table 1 was used instead of the unmodified block copolymer A-1.

Test pieces were prepared of the so-obtained compositions by compressionmolding, and the physical properties thereof were determined. Theobtained results are shown in Table 10. Furthermore, the adhesion ofeach composition to high density polyethylene was determined. Theobtained results are also shown in Table 10.

                                      TABLE 10                                    __________________________________________________________________________                                     Comparative                                                                          Comparative                                          Example 9                                                                           Example 10                                                                          Example 11                                                                          Example 9                                                                            Example 10                            __________________________________________________________________________    Composition (parts by weight)                                                 Modified hydrogenated                                                                        25    10    --    --     --                                    block copolymer C-1                                                           Modified hydrogenated                                                                        --    --    25    --     --                                    block copolymer C-3                                                           Unmodified block                                                                             --    --    --    25     --                                    copolymer A-1                                                                 Unmodified block                                                                             --    --    --    --     25                                    copolymer A-3                                                                 EVAL EP-E      75    90    75    75     75                                    Physical properties                                                           Melt index (200° C., 5 Kg                                                             5.1   9.6   6.8   24.8   25.6                                  load) (g/10 min)                                                              Izod impact strength*.sup.5                                                                  82.5  12.0  11.1  3.4    3.6                                   (Kg · cm/cm, notched)                                                Tensile strength*.sup.6 (yield                                                               330   420   382   340    356                                   point) (Kg/cm.sup.2)                                                          Tensile strength*.sup.8                                                                      270   318   306   314    320                                   (breaking point) (Kg/cm.sup.2)                                                Elongation (%)*.sup.8                                                                        58    75    63    24     21                                    Adhesion to high density                                                                     3.0   1.6   2.1   0.3    0.2                                   polyethylene*.sup.12 (T-peel-                                                 ing strength) (Kg/25 mm)                                                      __________________________________________________________________________     Note:                                                                         *.sup.5 and *.sup.6 See the Note under Table 5.                               *.sup.8 See the Note under Table 6.                                           *.sup.12 The adhesion to high density polyethylene was determined             according to JIS K6854.                                                  

As will be readily understood from the results shown in Table 10, thecomposition of Example 9 comprising the modified hydrogenated blockcopolymer has a tensile strength (yield point) substantially comparableto that of the composition of Comparative Example 9 comprising thecorresponding unmodified block copolymer, but the notched Izod impactstrength of the composition of Example 9 is extremely improved over thatof the comparative composition.

When the samples of the compositions of Example 9 and ComparativeExample 9 were observed by a phase contrast microscope, it was foundthat in the sample of Example 9, the modified block copolymer isuniformly dispersed in the form of particles having a size of about 0.5to about 2μ in the matrix of the ethylene-vinyl alcohol copolymer,wherease in the sample of Comparative Example 9, unmodified blockcopolymer particles having a size of about 5 to about 10μ or larger aredispersed. Accordingly, it has been confirmed that there is a distinctdifference of the compatibility between the two samples.

Furthermore, it has been confirmed that the composition of the presentinvention has an improved adhesion to polyethylene.

EXAMPLES 12 AND 13 AND COMPARATIVE EXAMPLES 11 AND 12

Each composition shown in Table 11 was prepared by using a mixingroller. Test pieces were prepared of the obtained composition bycompression molding. The physical properties thereof were determined.The obtained results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                                                   Com-     Com-                                                                 parative parative                                             Example                                                                              Example  Example  Example                                              12     13       11       12                                        ______________________________________                                        Composition                                                                   (parts by weight)                                                             Modified hydro-                                                                            75       90       --     --                                      genated block                                                                 copolymer C-1                                                                 Unmodified block                                                                           --       --       75     90                                      copolymer A-1                                                                 EVAL EP-E    25       10       25     10                                      Physical properties                                                           Melt index (200° C.,                                                                5.7      2.8      17.0   13.5                                    5 Kg load)                                                                    (g/10 min)                                                                    Hardness*.sup.8                                                                            89       87       87     87                                      300% modulus*.sup.8                                                                        86       82       44     31                                      (Kg/cm.sup.2)                                                                 Tensile strength*.sup.8                                                                    196      205      178    190                                     (breaking point)                                                              (Kg/cm.sup.2)                                                                 Oil resistance*.sup.30                                                                     23       48       53     54                                      (weight increase                                                              (%) (oil JIS No.                                                              3, 24 hours'                                                                  dipping)                                                                      Adhesion to high                                                                           7.4      6.2      1.6    1.7                                     density poly-                                                                 ethylene*.sup.12                                                              (T-peeling                                                                    strength)                                                                     (Kg/25 mm)                                                                    ______________________________________                                         Note:                                                                         *.sup.8 See the Note under Table 6.                                           *.sup.12 See the Note under Table 10.                                         *.sup.30 The oil resistance was determined according to JIS K6310.       

As will be readily understood from the results shown in Table 11, themodulus of the composition of the present invention is highly improvedand the oil resistance is remarkably improved by addition of a smallamount of the ethylene-vinyl alcohol copolymer. Moreover, the adhesionto polyethylene is improved with respect to the composition of thepresent invention.

EXAMPLES 14 THROUGH 16 AND COMPARATIVE EXAMPLES 13 THROUGH 15

Compositions of the present invention and comparative compositions wereobtained by mixing Paraplene P-22 SM (the trade name for a thermoplasticpolyurethane manufactured and sold by Nippon Polyurethane Co., Ltd.,Japan) as a polar thermoplastic polymer according to the recipe shown inTable 12 by means of a Brabender Plastograph.

Each of the obtained compositions was press-bonded at 180° C. to apolyvinyl chloride sheet or a high density polyethylene sheet and thepeeling strength was measured according to JIS K-6854. The obtainedresults are shown in Table 12.

                                      TABLE 12                                    __________________________________________________________________________                       Example                                                                            Example                                                                            Example                                                                            Comparative                                                                         Comparative                                                                         Comparative                                        14   15   16   Example 13                                                                          Example 14                                                                          Example 15                      __________________________________________________________________________    Composition                                                                          Modified hydrogenated                                                                     10   60   90   --    --    --                              (parts by                                                                            block copolymer C-1                                                    weight)                                                                              Unmodified block                                                                          --   --   --   10    60    90                                     copolymer A-1                                                          Polyurethane (Para-                                                                  90          40   10   90   40    10                                           plene P-22 SM)                                                         Adhesion to polyvinyl                                                                            9.2   8.9  6.0 8.0   2.8   0.9                             chloride (90° peeling strength)                                        (Kg/25 mm)                                                                    Adhesion to polyethylene                                                                         8.3  12.1 13.0 1.2   2.0   3.7                             (180° peeling strength)                                                (Kg/25 mm)                                                                    __________________________________________________________________________

As will be readily understood from the results shown in Table 12, thecomposition of the present invention has excellent adhesioncharacteristics to polyvinyl chloride and polyethylene sheets within abroad mixing ratio. In contrast, the adhesiveness of the comparativecomposition is inferior to that of the corresponding composition of thepresent invention.

EXAMPLES 17 AND 18

A mixture obtained by impregnating 100 parts by weight of thehydrogenated block copolymer B-1 used for formation of the modifiedhydrogenated block copolymer C-1 shown in Table 2 (obtained byhydrogenating the unmodified block copolymer A-1 shown in Table 1) with2.5 parts by weight of acrylic acid was homogeneously mixed with 0.1part by weight of Perhexa 25B [the trade name of2,5-dimethyl-2,5-di(tert-butylperoxy)hexane available from Nippon YushiK.K., Japan]. The obtained mixture was supplied into a screw typeextruder having a diameter of 20 mm (single, L/D=24) and the reactionwas carried out at a cylinder temperature of 210° C. to modify thehydrogenated block copolymer B-1. Unreacted acrylic acid was removedfrom the obtained modified hydrogenated block copolymer by heating underreduced pressure. Then, BHT was added as a stabilizer in an amount of0.5 part by weight per 100 parts by weight of the obtained polymer. Theso-obtained modified hydrogenated block copolymer is designated as "F-1".

A modified hydrogenated block copolymer was prepared in the same manneras described above except that the hydrogenated block copolymer B-3 usedfor formation of the modified hydrogenated block copolymer C-3 (obtainedby hydrogenating the unmodified block copolymer A-3 shown in Table 1)was used instead of the hydrogenated block copolymer B-1. The obtainedmodified hydrogenated block copolymer is designated as "F-2".

The analysis values of the so-obtained modified hydrogenated blockcopolymers are shown in Table 13.

                                      TABLE 13                                    __________________________________________________________________________    Modified       Amount (% by weight)                                           hydrogenated   of acrylic acid grafted                                                                   Melt index                                                                          Toluene-insoluble                            block  Polymer before                                                                        onto hydrogenated                                                                         (200° C.,                                                                    components content                           copolymer                                                                            hydrogenation                                                                         block copolymer                                                                           5 Kg load)                                                                          (% by weight)                                __________________________________________________________________________    F-1    A-1     2.05        1.1   0.05                                         F-2    A-3     1.87        0.9   0.05                                         __________________________________________________________________________

The amount of grafted onto the hydrogenated block copolymer was measuredby the neutralizing titration method using sodium methylate.

A resinous composition was obtained in the same manner as described inExamples 4 and 5 except that F-1 was used as the modified hydrogenatedblock copolymer.

Another resinous composition was obtained in the same manner asdescribed above except that F-2 was used as the modified hydrogenatedblock copolymer.

In the same manner as described in Examples 4 and 5, test pieces wereprepared of the so-obtained compositions, and the physical propertiesthereof were measured. The obtained results are shown in Table 14.

                  TABLE 14                                                        ______________________________________                                                         Example 17                                                                            Example 18                                           ______________________________________                                        Composition (parts by weight)                                                 Modified hydrogenated block                                                                      20        --                                               copolymer F-1                                                                 Modified hydrogenated block                                                                      --        20                                               copolymer F-2                                                                 Nylon 66           80        80                                               Physical properties                                                           Izod impact strength*.sup.5                                                                      32        29                                               (Kg · cm/cm, notched)                                                Tensile strength*.sup.6                                                                          670       650                                              (yield point) (Kg/cm.sup.2)                                                   Elongation*.sup.6 (%)                                                                            50        50                                               Transparency*.sup.7 (Haze) (%)                                                                   17.3      19.1                                             ______________________________________                                         Note: *.sup.5,*.sup.6 and *.sup.7 See the Note under Table 5.            

As will readily be understood from the results shown in Table 14, thecompositions of the present invention comprising modified hydrogenatedblock copolymers have improved impact strengths as compared with thecompositions of Comparative Examples 4 and 5 (see Table 7).

EXAMPLES 19 AND 20 AMD COMPARATIVE EXAMPLES 16 THROUGH 21

Compositions were prepared by mixing block copolymers shown in Table 15with the same nylon 66 as used in Examples 4 and 5 or the same EVAL EP-Eas used in Examples 9 through 11, and the Izod impact strength wasmeasured and the weatherability test and the heat aging resistance testwere carried out.

It was confirmed that the compositions of the present invention areexcellent in impact resistance, weatherability and resistance to heataging.

                                      TABLE 15                                    __________________________________________________________________________                       Comparative   Comparative                                                Example                                                                            Example  Example                                                                            Example                                                    19   16 17 18 20   19 20 21                                     __________________________________________________________________________    Composition (parts by weight)                                                 Block Copolymer                                                                        Kind C-3  A-3                                                                              B-3                                                                              D-2                                                                              C-2  A-2                                                                              B-2                                                                              D-1                                             Amount                                                                             20            25                                                Thermoplastic                                                                          Kind nylon 66      EVAL EP-E                                         Resin    Amount                                                                             80            75                                                Izod Impact Strength *5                                                                     24   7.0                                                                              8.1                                                                              22 85   3.4                                                                              3.9                                                                              82                                     (Kg · cm/cm, Notched)                                                Weatherability *3 (%)                                                                       72   42 71 45 83   54 80 59                                     Heat aging    80   51 78 55 77   48 75 51                                     Resistance *14 (%)                                                            __________________________________________________________________________     Note:-                                                                        *5 See the Note under Table 5.                                                *13 Before and after 500 hours' exposure (light irradiation only) in a        weatherometer (XWWR available from Atlas Co., U.S.A.), the Izod impact        strength (unnotched) of the test pieces was measured, and the                 weatherability was evaluated based on the Izod impact strength retention      after the exposure in the weatherometer, which was calculated according t     the following formula:                                                        Izod impact strength retention (weatherability (%)                            ##STR5##                                                                      *14 Before and after standing in air at 100° C. for one month, the     Izod impact strength (unnotched) of the test pieces was measured, and the     resistance to thermal deterioration was evaluated based on the Izod impac     strength retention, which was calculated according to the following           formula:                                                                      Izod impact strength retention (heat aging resistance) (%)                    =-                                                                            ##STR6##                                                                 

EXAMPLE 21 AND COMPARATIVE EXAMPLE 22

A modified hydrogenated block copolymer C-1' having maleic anhydridegrafted onto the hydrogenated block copolymer in an amount of 4.1% byweight was prepared in the same manner as adopted for the production ofthe modified hydrogenated block copolymer C-1 except that 7 parts byweight of maleic anhydride was incorporated into 100 parts by weight ofthe hydrogenated block copolymer B-1 (obtained by hydrogenating theunmodified block copolymer A-1 shown in Table 1).

A modified ethylene-propylene copolymer rubber G-1 was prepared in thesame manner as described above except that JSR EP57P (the trade name ofan ethylene-propylene copolymer rubber manufactured and sold by NipponGosei Gomu K.K., Japan) was used instead of the hydrogenated blockcopolymer B-1. The amount of maleic anhydride grafted was 3.0% byweight.

A resinous composition was obtained by mixing 20 parts by weight of theso-obtained modified hydrogenated block copolymer C-1' with 80 parts byweight of the same nylon-66 as used in Examples 4 and 5 by means of ascrew type extruder having a diameter of 30 mm (twin, L/D=28).

A comparative resinous composition was obtained in the same manner asdescribed above except that the modified ethylene-propylene copolymerrubber G-1 as prepared above was used instead of the modifiedhydrogenated block copolymer C-1'.

Test pieces were prepared of the obtained compositions by injectionmolding, and the physical properties thereof were determined.Futhermore, test pieces having a thickness of 0.5 mm were prepared ofthe compositions, and the transparency was measured. The obtainedresults are shown in Table 16. From the results shown in Table 16, it isapparent that the composition of the present invention is excellent intransparency and impact resistance.

                  TABLE 16                                                        ______________________________________                                                         Example                                                                              Comparative                                                            21     Example 22                                            ______________________________________                                        Composition (parts by weight)                                                 Modified hydrogenated                                                                            20       --                                                block copolymer C-1'                                                          Modified ethylene-propylene                                                                      --       20                                                copolymer rubber G-1                                                          Nylon 66           80       80                                                Physical Properties                                                           Izod impact strength*.sup.5                                                                      75       68                                                (Kg · cm/cm, notched)                                                Tensile strength*.sup.6                                                                          630      635                                               (yield point) (Kg/cm.sup.2)                                                   Elongation (%)*.sup.6                                                                            35       30                                                Transparency (Haze) (%).sup.*7                                                                   23.1     38.5                                              ______________________________________                                         Note: *.sup.5, *.sup.6 and *.sup.7 See the Note under Table 5.           

EXAMPLES 22 THROUGH 27 AND COMPARATIVE EXAMPLES 23 THROUGH 26

Compositions comprising Surlyn A-1706 (the trade name of a partiallymetal-crosslinked ethylene-acrylic acid copolymer available from Du PontCo., U.S.A.) as the component (a) were prepared by mixing according tothe recipe shown in Table 17 by means of rollers. The physicalproperties of the test pieces prepared from these compositions bycompression molding are shown in Table 17.

As will be readily understood from the results shown in Table 17, thecomposition of the present invention is improved over the comparativecompositions in tensile strength and oil resistance. Incidentally, inExamples 22 through 27, it was confirmed by an infraredspectrophotometer that the acid anhydride groups in the modified blockcopolymer participated in the ionic crosslinking.

Then, the adhesion of each composition to an aluminum plate wasexamined. It was found that the compositions of the present inventionare excellent over the comparative compositions in adhesive properties.The compositions of the present invention have a good adhesion evenafter immersion in water, and this is a great characteristic notpossessed by the comparative compositions.

                                      TABLE 17                                    __________________________________________________________________________                                    Comparative Example                                         Example No.       No.                                                         22 23 24 25 26 27 23 24 25 26                                   __________________________________________________________________________    Composition                                                                   Component (a)                                                                         Amount (%                                                                           30 20 10 30 20 10 30 20 10 --                                           by weight)                                                            Component (b)                                                                         Amount (%                                                                           70 80 90 70 80 90 70 80 90 100                                          by weight)                                                            Physical Properties                                                           300% Modulus*.sup.8 (Kg/cm.sup.2)                                                           64 57 55 70 65 60 51 45 44 35                                   Tensile strength*.sup.8                                                                     205                                                                              187                                                                              243                                                                              230                                                                              213                                                                              255                                                                              153                                                                              167                                                                              210                                                                              180                                  (breaking point) (Kg/cm.sup.2)                                                Oil resistande*.sup.28 (weight                                                              13 18 30 10 15 25 42 51 72 60                                   increase) (%)                                                                 Adhesion to                                                                           Before Im-                                                                          21.0                                                                             17.3                                                                             28.5                                                                             23.6                                                                             19.5                                                                             33.1                                                                             1.8                                                                              1.3                                                                              0.9                                                                              0.5                                  aluminium                                                                             mersion in                                                            plate*.sup.31 (peel-                                                                  Water                                                                 ing strength)                                                                         After Im-                                                                            6.3                                                                              5.2                                                                              8.4                                                                              7.1                                                                              5.7                                                                              9.8                                                                             0.2                                                                              0.2                                                                              0.1                                                                              0.1                                  (Kg/25 mm)                                                                            mersion in                                                                    Water                                                                 __________________________________________________________________________     Note:                                                                         *.sup.8 See the Note under Table 6.                                           *.sup.28 See the Note under Table 11.                                         *.sup.31 The adhesion was measured under the following conditions             according to the following method.                                            Measurement method: JIS K6854                                                 Bonding conditions: temperature of 200° C., compression pressure o     20 Kg/cm.sup.2                                                                Immersion conditions: room temperature (about 20° C.), 24 hours, i     water                                                                    

EXAMPLES 28 THROUGH 33 AND COMPARATIVE EXAMPLES 27 THROUGH 30

Compositions comprising Copolene QD-400 (the trade name of a partiallymetal-crosslinked ethylene-acrylic acid copolymer manufactured and soldby Asahi Down Co., Japan) as the component (a) were obtained by mixingaccording to the recipe shown in Table 18 by means of mixing rolls. Thephysical properties of the test pieces prepared of the obtainedcompositions by compression molding are shown in Table 18. Then, theadhesion of each composition to nylon (undrawn sheet of nylon 6) wasexamined. The obtained results are shown in Table 18.

From the results shown in Table 18, it is apparent that the compositionsof the present invention are excellent over the comparative compositionsin tensile strength and adhesiveness.

                                      TABLE 18                                    __________________________________________________________________________                                     Comparative                                                 Example No.       Example No.                                                 28 29 30 31 32 33 27 28 29                                     __________________________________________________________________________    Composition                                                                   Component (a)                                                                          Amount (%                                                                           80 70 60 80 70 60 80 70 60                                              by weight)                                                           Component (b)                                                                          Kind  C-5                                                                              C-6                                                                              C-2                                                                              E-2                                                                              E-3                                                                              E-1                                                                              A-4                                                                              A-5                                                                              A-2                                             Amount (%                                                                           20 30 40 20 30 40 20 30 40                                              by weight)                                                           Physical Properties                                                           Tensile Strength*.sup.6 (yield                                                               270                                                                              250                                                                              220                                                                              285                                                                              265                                                                              235                                                                              245                                                                              230 200                                   point) (Kg/cm.sup.2)                                                          Adhesion to                                                                            Before Im-                                                                          5.1                                                                              3.7                                                                              7.0                                                                              6.5                                                                              4.6                                                                              9.4                                                                              1.2                                                                              1.0                                                                              1.1                                    nylon sheet*.sup.32                                                                    mersion in                                                           (peeling strength)                                                                     Water                                                                (Kg/25 mm)                                                                             After Im-                                                                           3.4                                                                              2.8                                                                              5.4                                                                              4.7                                                                              3.1                                                                              6.2                                                                              0.2                                                                              0.1                                                                              0.1                                             mersion in                                                                    Water                                                                __________________________________________________________________________     Note:                                                                         *.sup. 6 See the Note under Table 5.                                          *.sup.32 The adhesion was measured under the following conditions             according to the following method.                                            Measurement method: JIS K6854                                                 Bonding conditions: temperature of 200° C., compression pressure o     20 Kg/cm.sup.2                                                                Immersion conditions: room temperature (about 20° C.), 24 hours, i     water                                                                    

EXAMPLES 34 THROUGH 43 AND COMPARATIVE EXAMPLES 30 THROUGH 41

Compositions comprising a thermoplastic polymer and a block copolymer,as shown in Table 19, were prepared. More specifically, 100 parts byweight of a thermoplastic polymer was sufficiently mixed with 10 partsby weight of a block copolymer by a Henschel mixer, and the mixture waspelletized by a screw type extruder having a diameter of 40 mm (single,L/D=28). A flat plate having a size of 120 mm×120 mm×3 mm was preparedfrom the pelletized composition by injection molding. The obtained flatplate was degreased with methyl alcohol, spray-coated with Acryca B160(the trade name of an acrylic resin paint available from Kawakami ToryoK.K., Japan), and naturally dried. In case of the composition comprisinga polyoxymethylene or nitrile resin as the thermoplastic polymer, theplate was, instead of being degreased with methyl alcohol, immersed in a0.1N hydrochloric acid solution for 30 seconds and spray-washed withwater.

Each resulting plate was subjected to the paint adhesion test. Theobtained results are shown in Table 19. As is apparent from the resultsshown in Table 19, the compositions of the present invention areexcellent in paint adhesion.

                  TABLE 19                                                        ______________________________________                                                                Kind of                                                        Kind of Block  Thermoplastic                                                                             Paint Ad-                                          Copolymer      Polymer*.sup.15                                                                           hesion*.sup.19                            ______________________________________                                        Example 34                                                                             modified hydro-                                                                              PO          ○                                           genated block                                                                 copolymer C-2                                                        Example 35                                                                             modified hydro-                                                                              PC          ⊚                                   genated block                                                                 copolymer C-2                                                        Example 36                                                                             modified hydro-                                                                              PS          ⊚                                   genated block                                                                 copolymer C-2                                                        Example 37                                                                             modified hydro-                                                                              NR          ○                                           genated block                                                                 copolymer C-2                                                        Example 38                                                                             modified hydro-                                                                              PPE         ⊚                                   genated block                                                                 copolymer C-2                                                        Example 39                                                                             modified hydro-                                                                              GPPE        ⊚                                   genated block                                                                 copolymer C-2                                                        Example 40                                                                             modified hydro-                                                                              PPS         ⊚                                   genated block                                                                 copolymer C-2                                                        Example 41                                                                             modified hydro-                                                                              PC + PET*.sup.16                                                                          ○                                           genated block                                                                 copolymer C-2                                                        Example 42                                                                             modified hydro-                                                                              PS + PA*.sup.17                                                                           ○                                           genated block                                                                 copolymer C-2                                                        Example 43                                                                             modified hydro-                                                                              PO + TPET*.sup.18                                                                         ○                                           genated block                                                                 copolymer C-2                                                        Comparative                                                                            unmodified block                                                                             PO          X                                         Example 30                                                                             copolymer A-2                                                        Comparative                                                                            unmodified block                                                                             PC          Δ                                   Example 31                                                                             copolymer A-2                                                        Comparative                                                                            unmodified block                                                                             PS          Δ                                   Example 32                                                                             copolymer A-2                                                        Comparative                                                                            unmodified block                                                                             NR          X                                         Example 33                                                                             copolymer A-2                                                        Comparative                                                                            unmodified block                                                                             PPE         ○                                  Example 34                                                                             copolymer A-2                                                        Comparative                                                                            unmodified block                                                                             PPS         Δ                                   Example 35                                                                             copolymer A-2                                                        Comparative                                                                            hydrogenated block                                                                           PO          X                                         Example 36                                                                             copolymer B-2                                                        Comparative                                                                            hygrogenated block                                                                           PC          Δ                                   Example 37                                                                             copolymer B-2                                                        Comparative                                                                            hydrogenated block                                                                           PS          Δ                                   Example 38                                                                             copolymer B-2                                                        Comparative                                                                            hydrogenated block                                                                           NR          X                                         Example 39                                                                             copolymer B-2                                                        Comparative                                                                            hydrogenated block                                                                           PPE         ○                                  Example 40                                                                             copolymer B-2                                                        Comparative                                                                            hydrogenated block                                                                           PPS         Δ                                   Example 41                                                                             copolymer B-2                                                        ______________________________________                                        Note:                                                                         *.sup.15 The thermoplastic polymers used are as follows (PS,                  PPE and PPS are products of companies in U.S.A. and other                     resins are products of Japanese companies):                                   Abbrevi-                                                                      ation  Thermoplastic Polymer                                                                         Maker      Trade name                                  PC     polycarbonate   Teijin Kasei                                                                             Panlite                                                                       L-1225                                      PS     polysulfone     ICI        Polyether                                                                     Sulfone 200P                                PPE    polyphenylene ether                                                                           General    Noryl 701                                                          Electric                                               GPPE   styrene-grafted Asahi-Dow  Xylon 500H                                         polyphenylene ether                                                    PPS    polyphenylene sulfide                                                                         Phillips   Ryton R-6                                                          Petroleum                                              PBT    polybutylene    Toray      PBT 1041                                           terephthalate                                                          TPET   thermoplastic   Toyobo     Pelprene                                           polyester                  P150B                                       PA     polyamide       Toray      Amilan                                                                        CM-1017                                     ABS    acrylonitrile-butadi-                                                                         Asahi-Dow  Stylac 181                                         ene styrene copolymer                                                  HIPS   impact-resistant                                                                              Asahi-Dow  Styron 492                                         rubber modified                                                               polystyrene                                                            PO: polyoxymethylene (polyoxymethylene diacetate having                       a melt index of about 10 g/10 min as measured at                              210° C. under a load of 2.16 kg was used)                              NR: nitrile resin [acrylonitrile/styrene (90/10)                              copolymer having a melt index of about 1 g/10 min                             as measured at 190° C. under a load of 12.5 kg was used]               *.sup.16 A mixture of PC/PET (2/1 weight ratio) was used as the               thermoplastic polymer.                                                        *.sup.17 A mixture of PS/PA (2/1 weight ratio) was used as the                thermoplastic polymer.                                                        *.sup.18 A mixture of PO/TPET (4/1 weight ratio) was used as                  thermoplastic polymer.                                                        *.sup.19 Eleven cut lines having an interval of 1 mm were formed              with a knife on the coated surface of the flat plate in                       both the longitudinal direction and the lateral direction                     to form 100 cut squares. A pressure sensitive adhesive cellophane             tape was applied to the coated surface and the tape was                       peeled off in the vertical direction. The adhesiveness                        was evaluated based on the number of cut squares peeled                       together with the tape.                                                       ⊚:  up to 10 of peeled squares                                  ○  : 11 to 20 of peeled squares                                       Δ:  21 to 40 of peeled squares                                          X: 41 or more of peeled squares                                           

EXAMPLES 44 THROUGH 47 AND COMPARATIVE EXAMPLES 42 THROUGH 53

Compositions comprising a thermoplastic polymer and a block copolymer,shown in Table 20, were prepared in the following manner. Namely, 100parts by weight of a thermoplastic polymer was mixed with 50 parts byweight of a block copolymer by a screw type extruder having a diameterof 40 mm (single L/D=28) and the mixture was pelletized. Test pieceswere prepared of the pelletized composition by injection molding. TheIzod impact strength and gloss thereof were measured and theweatherability and heat aging tests were carried out. The obtainedresults are shown in Table 20. In Table 20, there are also shown thevalues of the gloss measured for the test pieces of the compositioncomprising the ionic crosslinking product E-3 of the modified blockcopolymer C-6, which was used as a block copolymer. From the resultsshown in Table 20, it is seen that the compositions of the presentinvention are excellent in weatherability and heat aging resistance asexpressed in strength retention.

                                      TABLE 20                                    __________________________________________________________________________                       Izod                                                                          impact            Heat                                                   Thermo-                                                                            Strength *5 Weather-                                                                            Aging                                    Block         plastic                                                                            (Kg · cm/cm,                                                                Gloss *20                                                                          ability *21                                                                         Resistance *14                           Copolymer     Polymer                                                                            notched                                                                              (%)  (%)   (%)                                      __________________________________________________________________________    Example 44                                                                          modified hy-                                                                          PC   38.6   70 (75)                                                                            73    78                                             drogenated                                                                    block copoly-                                                                 mer C-6                                                                 Example 45                                                                          modified hy-                                                                          PS   10.4   61 (68)                                                                            76    80                                             drogenated                                                                    block copoly-                                                                 mer C-6                                                                 Example 46                                                                          modified hy-                                                                          GPPE 29.5   71 (77)                                                                            74    87                                             drogenated                                                                    block copoly-                                                                 mer C-6                                                                 Example 47                                                                          modified hy-                                                                          PPS  4.6    62 (70)                                                                            79    85                                             drogenated                                                                    block copoly-                                                                 mer C-6                                                                 Comparative                                                                         unmodified                                                                            PC   29.1   63   31    45                                       Example 42                                                                          block copoly-                                                                 mer A-5                                                                 Comparative                                                                         unmodified                                                                            PS   6.3    55   34    47                                       Example 43                                                                          block copoly-                                                                 mer A-5                                                                 Comparative                                                                         unmodified                                                                            GPPE 24.2   66   36    55                                       Example 44                                                                          block copoly-                                                                 mer A-5                                                                 Comparative                                                                         unmodified                                                                            PPS  2.5    57   40    54                                       Example 45                                                                          block copoly-                                                                 mer A-5                                                                 Comparative                                                                         hydrogenated                                                                          PC   30.0   64   72    76                                       Example 46                                                                          block copoly-                                                                 mer B-5                                                                 Comparative                                                                         hydrogenated                                                                          PS   6.9    54   74    79                                       Example 47                                                                          block copoly-                                                                 mer B-5                                                                 Comparative                                                                         hydrogenated                                                                          GPPE 25.0   67   74    87                                       Example 48                                                                          block copoly-                                                                 mer B-5                                                                 Comparative                                                                         hydrogenated                                                                          PPS  2.8    55   79    85                                       Example 49                                                                          block copoly-                                                                 mer B-5                                                                 Comparative                                                                         modified unhy-                                                                        PC   34.5   70   32    47                                       Example 50                                                                          drogenated                                                                    block copoly-                                                                 mer D-3                                                                 Comparative                                                                         modified unhy-                                                                        PS   8.5    60   34    47                                       Example 51                                                                          drogenated                                                                    block copoly-                                                                 mer D-3                                                                 Comparative                                                                         modified unhy-                                                                        GPPE 27.0   71   38    56                                       Example 52                                                                          drogenated                                                                    block copoly-                                                                 mer D-3                                                                 Comparative                                                                         modified unhy-                                                                        PPS  3.5    60   41    54                                       Example 53                                                                          drogenated                                                                    block copoly-                                                                 mer D-3                                                                 __________________________________________________________________________     Note:-                                                                        *5 See the Note under Table 5                                                 *14 See the Note under Table 15.                                              *20 The gloss was measured according to the method of JIS Z8741. Each         parenthesized value in Table 20 is the value of gloss measured with           respcet to the composition comprising the ionic crosslinking product E3 o     the modified hydrogenated block copolymer C6 instead of the copolymer C6.     *21 After and before 1000 hours' exposure (light irradiation only) in a       weatherometer (XWWR manufactured and sold by Atlas Co., U.S.A.), the Izod     impact strength (unnotched) of test pieces was measured, and the Izod         impact retention after the exposure in the weatherometer was calculated       according to the following formula:                                           Izod impact strength retention (weatherability) (%)                           =-                                                                            ##STR7##                                                                 

EXAMPLES 48 THROUGH 51 AND COMPARATIVE EXAMPLES 54 THROUGH 57

Compositions of the present invention and comparative compositions wereprepared according to the recipes shown in Table 21 by using a screwtype extruder having a diameter of 40 mm (single, L/D=28). Test pieceswere prepared of the obtained compositions by injection molding, and theIzod impact strength thereof was measured. The obtained results areshown in Table 21. From the results shown in Table 21, it is seen thatthe composition of the present invention is excellent in impactresistance. Incidentally, polystyrene having a weight average molecularweight of about 220,000 was used in Example 50 and Comparative Example56.

                                      TABLE 21                                    __________________________________________________________________________                        Example No.    Comparative Example No.                                        48 49  50  51  54 55  56  57                              __________________________________________________________________________    Block Co-                                                                             Kind        Modified hydrogenated                                                                        unmodified block                           polymer             block copolymer C-5                                                                          copolymer A-4                                      Amount (%   10 20  20  10  10 20  20  10                                      by weight)                                                            Thermoplastic                                                                         First Kind  PC PS  GPPE                                                                              PPS PC PS  GPPE                                                                              PPS                             polymer*.sup.15                                                                       Component                                                                           Amount (%                                                                           70 60  65  70  70 60  65  70                                            by weight)                                                              Second                                                                              Kind  ABS                                                                              HIPS                                                                              poly-                                                                             HIPS                                                                              ABS                                                                              HIPS                                                                              poly-                                                                             HIPS                                    Component          styrene        styrene                                           Amount (%                                                                           20 20  15  20  20 20  15  20                                            by weight)                                                      Izod Impact         46.1                                                                             19.0                                                                              35.3                                                                              16.5                                                                              35.2                                                                             13.4                                                                              29.6                                                                              10.7                            Strength*.sup.5 (Kg · cm/                                            cm/ notched)                                                                  __________________________________________________________________________     Note:                                                                         *.sup.5 See the Note under Table 5.                                           *.sup.15 See the Note under Table 19.                                    

EXAMPLES 52 AND 53 AND COMPARATIVE EXAMPLES 58 AND 59

The unmodified block copolymer A-5 was hydrogenated according to thesame method as adopted for production of the hydrogenated blockcopolymers B-1 through B-6 to obtain two hydrogenated block copolymershaving hydrogenation degrees of about 86% and about 60%, respectively.The hydrogenated block copolymers were modified according to the samemethod as adopted for production of the modified hydrogenated blockcopolymer C-6 to obtain modified hydrogenated block copolymers C-6' andC-6" having a hydrogenation degree different from that of C-6.Compositions comprising the modified hydrogenated block copolymer C-6,the obtained modified hydrogenated block copolymer C-6' or C-6" or themodified unhydrogenated block copolymer D-3 were obtained according tothe recipe shown in Table 22 by using a screw type extruder having adiameter of 40 mm (single, L/D=28). Test pieces were prepared of theobtained compositions by injection molding, and the weatherability andheat aging tests were carried out. The obtained results are shown inTable 22.

From the results shown in Table 22, it is seen that when a modifiedblock copolymer prepared from a block copolymer having a hydrogenationdegree lower than 80% (an ethylenic unsaturation degree exceeding 20%)is used, the weatherability and resistance to heat aging are degraded.

                  TABLE 22                                                        ______________________________________                                                                 Comparative                                                         Example   Example                                                             52   53       58      59                                       ______________________________________                                        Unhydrogenated polymer                                                                         A-5                                                          used for formation of                                                         modified block copolymer                                                      Hydrogenation degree (%)                                                                       90     86       60    0                                      Amount (% by weight) of                                                                        1.2    1.3      1.3   1.2                                    maleic anhydride grafted                                                      onto the block copolymer                                                      Composition                                                                            modified block                                                                            C-6    C-6'   C-6"  D-3                                  (parts by                                                                              copolymer                                                            weight)  amount      50     50     50    50                                            thermoplastic                                                                             PC     PC     PC    PC                                            polymer*.sup.15                                                               amount      100    100    100   100                                  Weatherability*.sup.21 (%)                                                                     73     70       53    32                                     Heat aging       78     71       55    47                                     resistance*.sup.14 (%)                                                        ______________________________________                                         Note:                                                                         *.sup.15 See the Note under Table 19.                                         *.sup.21 See the Note under Table 20.                                         *.sup.14 See the Note under Table 15.                                    

EXAMPLES 54 AND 55

Compositions of the present invention containing a glass fiber wereprepared according to the recipe shown in Table 23 by using a screw typeextruder having a diameter of 30 mm (twin, L/D=28). Test pieces wereprepared of the obtained compositions by injection molding, and the Izodimpact strength was measured. The obtained results are shown in Table23.

                  TABLE 23                                                        ______________________________________                                                         Example 54                                                                            Example 55                                           ______________________________________                                        Composition (parts by weight)                                                 modified hydrogenated block                                                                      30        --                                               copolymer C-6                                                                 modified hydrogenated block                                                                      --        10                                               copolymer C-4                                                                 thermoplastic polymer PS*.sup.15                                                                 40        --                                               thermoplastic polymer PPE*.sup.15                                                                --        70                                               glass fiber*.sup.22                                                                              30        20                                               Physical Property                                                             Izod impact strength*.sup.5                                                                      12.5      23.1                                             (Kg · cm/cm, notched)                                                ______________________________________                                         Note:                                                                         *.sup.5 See the Note under Table 5.                                           *.sup.15 See the Note under Table 19.                                         *.sup.22 CS 99A401 (the trade name of a glass fiber manufactured and sold     by Nittobo Co., Japan) was used.                                         

EXAMPLES 56 THROUGH 63 AND COMPARATIVE EXAMPLES 60 THROUGH 66

Compositions of the present invention and comparative compositionscomprising a block copolymer and a thermoplastic polymer, shown in Table24, were prepared according to the recipe shown below by using a screwtype extruder having a diameter of 30 mm (twin, L/D=28) for kneading.

    ______________________________________                                                               Amount                                                 Composition Recipe     (parts by weight)                                      ______________________________________                                        modified hydrogenated block copolymer                                                                100                                                    C-2 or unmodified block copolymer A-2                                         thermoplastic polymer*.sup.23                                                                        50                                                     Shellflex 311 (the trade name of a                                                                   50                                                     naphthene type process oil manufac-                                           tured and sold by Sankyo Yuka                                                 Co., Ltd., Japan)                                                             titanium oxide          1                                                     stabilizer*.sup.24     0.7                                                    ______________________________________                                         Note:                                                                         *.sup.23 A powdery product having a particle size of about 50 mesh, which     was obtained by freezepulverizing the pelletized thermoplastic polymer,       was used.                                                                     *.sup.24 2,2'-Methylene-bis(4-methyl-6-tert-butylphenol) was used as the      stabilizer.                                                              

Test pieces of the obtained compositions were prepared by molding, andthe tensile strength, abrasion resistance and compression permanentstrain thereof were determined. The obtained results are shown in Table24.

From the results shown in Table 24, it is seen that the composition ofthe present invention is excellent over the comparative compositioncomprising an unmodified block copolymer in tensile strength, abrasionresistance and resistance to compression permanent strain.

According to the method described in the Note *10 under Table 6, theweatherability test was carried out. It was found that the test piecesof the compositions of Examples 56 through 63, after the weatherabilitytest, substantially retained the characteristics and rubbery elasticity,while with respect to the test pieces of the compositions of ComparativeExamples 62 through 68, the elongation retention at the tensile test waslower than 30% and the rubbery elasticity was lost, showing considerabledeterioration.

                                      TABLE 24                                    __________________________________________________________________________                               Abrasion                                                                           Compression Permanent                                       Thermo- Tensile*.sup.8                                                                     Resis-                                                                             Strain (%)*.sup.26                                   Block Co-                                                                            plastic Strength                                                                           tance*.sup.25                                                                              *.sup.27                                                                          *.sup.27                                 polymer                                                                              polymer (Kg/cm.sup.2)                                                                      (index)                                                                            20° C.                                                                     60° C.                                                                     20° C.                                                                     60° C.                     __________________________________________________________________________    Example 56                                                                           modified by-                                                                         PO      128  135  20  33  12  22                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 57                                                                           modified hy-                                                                         PC      140  150  18  30  10  20                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 58                                                                           modified hy-                                                                         PS      133  145  17  25  10  12                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 59                                                                           modified hy-                                                                         NR      125  130  21  32  11  21                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 60                                                                           modified hy-                                                                         PPE     140  160  17  27  12  20                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 61                                                                           modified hy-                                                                         PPS     137  145  18  26  10  16                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 62                                                                           modified hy-                                                                         PC + PBT*.sup.28                                                                      131  130  19  32  11  21                                       drogenated                                                                    block co-                                                                     polymer C-2                                                            Example 63                                                                           modified hy-                                                                         PS + PA*.sup.28                                                                       128  130  20  35  13  20                                Comparative                                                                          unmodified                                                                           PO       93   80  36  58  --  --                                Example 60                                                                           block co-                                                                     polymer A-2                                                            Comparative                                                                          unmodified                                                                           PC      102  100  30  53  --  --                                Example 61                                                                           block co-                                                                     polymer A-2                                                            Comparative                                                                          unmodified                                                                           PS       97   90  34  47  --  --                                Example 62                                                                           block co-                                                                     polymer A-2                                                            Comparative                                                                          unmodified                                                                           NR       90   70  28  51  --  --                                Example 63                                                                           block co-                                                                     polymer A-2                                                            Comparative                                                                          unmodified                                                                           PPE     100  100  32  54  --  --                                Example 64                                                                           block co-                                                                     polymer A-2                                                            Comparative                                                                          unmodified                                                                           PPS      98   90  34  51  --  --                                Example 65                                                                           block co-                                                                     polymer A-2                                                            Comparative                                                                          unmodified                                                                           poly-   120  100  27  63  --  --                                Example 66                                                                           block co-                                                                            styrene                                                                polymer A-2                                                            __________________________________________________________________________     Note:                                                                         *.sup.25 The abrasion resistance was determined according to the method o     ASTM D2228, and there is shown a relative value calculated based on tne       supposition that the abrasion of the composition of Comparative Example 6     comprising polystyrene as t he thermoplastic polymer was 100. A larger        value indicates a better abrasion resistance.                                 *.sup.26 The measurement was carried out at a compression ratio of 2.5%       for a compression time cf 22 hours according to JIS K6301.                    *.sup.27 At the step of extrusion kneading, 0.5 part by weight of zinc        stearate was further added per 100 parts by weight of the sample C2, and      the compression permanent strain of the resulting composition comprising      the ionic crosslinking product o f the modified block copolymer was           measured.                                                                     *.sup.28 A mixture of PC/PBT (mixing weight ratio = 2/1) and a mixture of     PS/PA (mixing weight ratio = 2/1) were used as the thermoplastic polymer.

EXAMPLES 64 AND 65 AND COMPARATIVE EXAMPLE 67

Compositions comprising Surlyn A-1706 (the trade name of a partiallymetal-crosslinked ethylene-acrylic acid copolymer available from Du PontCo., U.S.A.) as the component (a) were prepared according to the recipeshown in Table 25 by using mixing rolls. Test pieces of the obtainedcompositions were prepared by compression molding and the Izod impactstrength thereof was measured to obtain results shown in Table 25, fromwhich it is seen that the compositions of the present invention have anexcellent Izod impact strength.

                  TABLE 25                                                        ______________________________________                                                      Example                                                                              Example   Comparative                                                  64     65        Example 67                                     ______________________________________                                        Composition                                                                   component (a)                                                                           amount (% 20       20      20                                                 by weight)                                                          component (b)                                                                           kind      C-7      E-4     B-6                                                amount (% 80       80      80                                                 by weight)                                                          Izod Impact Strength*.sup.5                                                                   6.5      8.7       4.2                                        Kg · cm/cm, notched)                                                 ______________________________________                                         Note:                                                                         *.sup.5 See the Note under Table 5.                                      

EXAMPLES 66 THROUGH 68 AND COMPARATIVE EXAMPLES 68 THROUGH 72

Compositions comprising a modified block copolymer and Evaflex 150 (thetrade name of an ethylene-vinyl acetate copolymer available from MitsuiPolychemical Co., Ltd., Japan), as shown in Table 26, were prepared byusing a screw type extruder having a diameter of 40 mm (single, L/D=28),and these compositions were tested with respect to the adhesiveness toan aluminum plate. The obtained results are shown in Table 26.

The modified hydrogenated block copolymer C-8 shown in Table 26 wasprepared in the following manner.

A block copolymer of the S-B-S type having a styrene content of 20% byweight, a number average molecular weight of about 100,000 and a vinylcontent in the butadiene block of about 35% was hydrogenated to obtain ahydrogenated block copolymer B-7 (having a hydrogenation degree of about90%). The obtained copolymer B-7 was modified with maleic anhydride toobtain a modified hydrogenated block copolymer C-8 (the amount of maleicanhydride grafted onto the hydrogenated block copolymer was 0.25% byweight).

                                      TABLE 26                                    __________________________________________________________________________                   Example No.                                                                            Comparative Example No.                                              66 67 68 68 69 70 71 72                                        __________________________________________________________________________    Composition                                                                   Component (a)                                                                          Amount (%                                                                           40 70 20 40 70 20 100                                                                              --                                        Evaflex 150                                                                            by weight)                                                           Component (b)                                                                          Kind  C-1                                                                              C-1                                                                              C-8                                                                              B-1                                                                              B-1                                                                              B-7                                                                              -- B-1                                                Amount (%                                                                           60 30 80 60 30 80 -- 100                                                by weight)                                                           Adhesion to                                                                            Before Im-                                                                          13.2                                                                             6.5                                                                              3.5                                                                              1.5                                                                              1.1                                                                              1.7                                                                              1.0                                                                              2.0                                       aluminium*.sup.31                                                                      mersion in                                                           (peeling Water                                                                strength)                                                                              After Im-                                                                            3.1                                                                             1.8                                                                              1.9                                                                              0.3                                                                              0.2                                                                              0.4                                                                              0.1                                                                              0.5                                       (Kg/25 mm)                                                                             mersion in                                                                    Water                                                                __________________________________________________________________________     Note:                                                                         *.sup.31 See the Note under Table 17.                                    

EXAMPLE 69

The hydrogenated block copolymer B-1 was supplied into a screw typeextruder having a diameter of 30 mm (twin, L/D=28), and simultaneously,0.1 part by weight of Perhexa 25B [the trade name of2,5-dimethyl-2,5-di(t-butylperoxy)hexane available from Nippon YushiK.K., Japan] and 35 parts by weight of maleic anhydride, per 100 partsby weight of the hydrogenated block copolymer B-1, were supplied throughthe side supply inlet provided on the cylinder portion of the extruder.The maleinization reaction was carried out at a cylinder temperature of250° C. The obtained block copolymer (C-9) was treated and analyzed inthe same manner as described hereinbefore. It was found that the amountof maleic anhydride grafted onto the hydrogenated block copolymer was18.5% by weight.

Compositions were prepared in the same manner as described in Examples34 through 47 except that the copolymer C-9 was used as the modifiedhydrogenated block copolymer, and the physical properties of thecompositions were examined. It was found that this composition isexcellent in paint adhesion, impact resistance, gloss, weatherabilityand resistance to heat aging as well as the compositions obtained inExamples 34 through 47.

Probability of Utilization in Industry

As will be apparent from the foregoing description, since the modifiedblock copolymer composition of the present invention is a compositioncomprising a thermoplastic polymer and a modified block copolymer havinga very good compatibility with each other, the composition of thepresent invention is very homogeneous and is excellent over theconventional mixtures of different polymers in mechanicalcharacteristics, and furthermore, the composition of the presentinvention has an excellent weatherability and heat aging resistance.Accordingly, it is expected that the composition of the presentinvention will be effectively used in various fields. As specific usesnow considered, there can be mentioned materials for machine parts,automobile parts, electrical parts, toys, industrial parts, belts,hoses, shoes, medical appliances, shock-absorbing rubber articles, dailynecessaries, miscellaneous goods, construction articles, sheets, films,blow-molded articles, solution-type adhesives, hot melt adhesives,tackifiers and adhesive layers of laminated articles.

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the present invention, and allsuch modifications as would be obvious to one skilled in the art areintended to be included within the scope of the following claims.

What is claimed is:
 1. A modified block copolymer compositioncomprising:(a) a thermoplastic polymer component selected from the groupconsisting of members (i) and (ii),said member (i) being at least onethermoplastic polymer selected from the group consisting of polarthermoplastic polymers each containing at least one polar functionalgroup, polyoxymethylenes, polycarbonates, modified polycarbonates,polysulfones, modified polysulfones, nitrile polymers, polyphenyleneethers, modified polyphenylene ethers, polyarylene sulfides and modifiedpolyarylene sulfides, said polar thermoplastic polymers being exclusiveof polyamides, said member (ii) being a polyamide and at least onethermoplastic polymer selected from the group consisting of polarthermoplastic polymers each containing at least one polar functionalgroup, polyoxymethylenes, polycarbonates, modified polycarbonates,polysulfones, modified polysulfones, nitrile polymers, polyphenyleneethers, modified polyphenylene ethers, polyarylene sulfides and modifiedpolyarylene sulfides, said polar thermoplastic polymers being exclusiveof polyamides; and (b) at least one modified block copolymer whichcomprises a base block copolymer of at least one monovinyl substitutedaromatic hydrocarbon polymer block A and at least one olefin compoundpolymer block B having an ethylenic unsaturation degree not exceeding20%, said base block copolymer having at least one molecular unitgrafted thereto, said at least one molecular unit containing at leastone member selected from a carboxylic acid group and groups derivedtherefrom, said monovinyl substituted aromatic hydrocarbon beingcontained in said base block copolymer in an amount of 5 to 60% byweight based on said base block copolymer;said thermoplastic polymer (a)being present in a weight ratio of 70:30 up to 98:2 relative to saidmodified block copolymer (b); said polar thermoplastic polymersexcluding said modified block copolymer (b).
 2. A composition accordingto claim 1, wherein said modified polycarbonates, said modifiedpolysulfones, said modified polyphenylene ethers and said modifiedpolyarylene sulfides are respectively blends of polycarbonates,polysulfones, polyphenylene ethers and polyarylene sulfides with analkyl aromatic hydrocarbon polymer and/or an alkenyl aromatichydrocarbon copolymer.
 3. A composition according to claim 1, whereinsaid polar thermoplastic polymers each contain at least one polarfunctional group selected from the group consisting of an amino group,hydroxyl group, thiol group, carboxyl group, isocyanate group, epoxygroup, urethane group, ether group, amide group, ammonium salt group andmetal carboxylate group.
 4. A composition according to claim 3, whereinsaid polar thermoplastic polymers are thermoplastic polyesters.
 5. Acomposition according to claim 3, wherein said polar thermoplasticpolymers are thermoplastic polyurethanes.
 6. A composition according toclaim 3, wherein said polar thermoplastic polymers are polyvinylalcohols.
 7. A composition according to claim 3, wherein said polarthermoplastic polymers are polyvinyl esters.
 8. A composition accordingto claim 3, wherein said polar thermoplastic polymers are ionomers ofsubstrate copolymers of αβ-unsaturated carboxylic acids and othermonomers, said ionomers having carboxylic acid groups ionicallycrosslinked through at least one metal ion selected from the groupconsisting of monovalent, divalent and trivalent metal ions.
 9. Acomposition according to claim 1, wherein said molecular unit containingat least one member selected from a carboxylic acid group and groupsderived therefrom is grafted onto said base block copolymer in amount of0.05 to 30 parts by weight per 100 parts by weight of said base blockcopolymer.
 10. A composition according to claim 1, wherein said at leastone modified block copolymer is a product obtained by the reaction ofthe base block copolymer of at least one monovinyl substituted aromatichydrocarbon polymer block A and at least one olefin compound polymerblock B having an ethylenic unsaturation degree not exceeding 20% withat least one modifying agent selected from the group consisting ofunsaturated carboxylic acids and derivatives thereof.
 11. A compositionaccording to claim 10, wherein said product is one obtained by theaddition reaction of the base block copolymer with at least onemodifying agent selected from the group consisting of unsaturatedcarboxylic acids and derivatives thereof, said base block copolymerbeing a product produced by selectively hydrogenating a precursory blockcopolymer comprising at least one monovinyl substituted aromatichydrocarbon polymer block and at least one polymer block composed mainlyof a conjugated diene compound at its conjugated diene compound moietyto the extent that the ethylenic unsaturation degree of the polymerblock composed mainly of the conjugated diene compound is 20% or less.12. A composition according to claim 11, wherein the conjugated dienecompound moiety of said precursory block copolymer has a vinylic contentof 10 to 80%.
 13. A composition according to claim 12, wherein the vinylcontent is 25 to 65%.
 14. A composition according to claim 11, whereinsaid at least one modifying agent is selected from the group consistingof maleic acid, maleic anhydride, maleic acid esters, maleic acidamides, maleic acid imides, fumaric acid, fumaric acid esters, fumaricacid amides, fumaric acid imides, itaconic acid, itaconic anhydride,itaconic acid esters, itaconic acid amides, itaconic acid imides,halogenated maleic acid, halogenated maleic anhydride, halogenatedmaleic acid esters, halogenated maleic acid amides, halogenated maleicacid imides, cis-4-cyclohexene-1,2-dicarboxylic acid,cis-4-cyclohexene-1,2-dicarboxylic anhydride,cis-4-cyclohexene-1,2-dicarboxylic acid esters,cis-4-cyclohexene-1,2-dicarboxylic acid amides,cis-4-cyclohexene-1,2-dicarboxylic acid imides,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid esters,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid amines,endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid imides, acrylicacid, acrylic esters, acrylic amide, methacrylic acid, methacrylicesters and methacrylic amide.
 15. A composition according to claim 1,wherein said modified block copolymer is ionically crosslinked throughat least one metal ion selected from the group consisting of monovalent,divalent and trivalent metal ions to form an ionically crosslinkedmodified block copolymer.
 16. A composition according to claim 15,wherein the ionical crosslinking of said modified block copolymerthrough said metal ion is made in a ratio of 0.1:3.0, said ratio beinggiven in terms of a molar ratio of metal ion relative to the total ofcarboxylic acid group and groups derived therefrom contained in saidmodified block copolymer.
 17. A composition according to claim 15,wherein said metal ion is at least one member selected from the groupconsisting of lithium, sodium, potassium, magnesium, calcium, zinc andaluminum ions.